201226632 六、發明說明： 【發明所屬之技術領域】 本發明關於自鑛敷排水回收貴金屬離子之方法，特別 地關於可自鍍敷回收槽及鍍敷洗淨槽的鍍敷排水中，高效 率回收貴金屬離子，而且可抑制鍍敷被處理物的性能不良 之自鎪敷排水回收貴金屬離子之方法。 【先前技術】 貴金屬由於物性特性、可靠性、美觀等優異，而是工 業上非常有用的材料，作爲鍍敷材，在以電子零件或印刷 配線板等的電子機器領域爲首的廣泛領域中被利用。另一 方面，貴金屬係稀少地存在，而爲非常高價的材料。因此 ，要求盡可能地回收及再利用鍍敷排水中所含有的貴金屬 0 —般地，鍍敷排水係分爲來自鍍敷槽、鍍敷回收槽及 鎪敷洗淨槽之排水。鍍敷回收槽由於作爲鍍敷槽的鍍敷處 理後之一次洗淨槽的角色，故在來自鍍敷回收槽的排水中 ，含有比鍍敷槽的排水還低濃度的貴金屬離子。又，鍍敷 洗淨槽由於作爲二次或三次洗淨槽的角色，故在來自鍍敷 洗淨槽的排水中，含有比鍍敷回收槽的排水還低濃度的貴 金屬離子。如此地，自各槽所排出的鑛敷排水之貴金屬離 子濃度係不同。 又，要求鍍敷回收槽及鍍敷洗淨槽中的過剩地附著於 鑛敷被處理物之貴金屬離子或鹽成分的洗出，更且抑制鍍 -5- 201226632 敷液的成分之有機物所致的黴菌或細菌之發生、鍍敷回收 槽的槽內之管理。 作爲自鍍敷排水回收貴金屬離子之方法，一般已知電 解回收法、樹脂回收法及活性碳吸附回收法。電解回收法 雖然對於自貴金屬離子的濃度高之鍍敷排水中回收貴金屬 離子者優異，但是若爲低濃度的鍍敷排水，則即使將電解 槽內循環，電流密度也不會上升，而貴金屬離子的回收效 率變差。另一方面，樹脂回收法及活性碳吸附回收法，雖 然對於自貴金屬離子濃度低的鍍敷排水中回收貴金屬離子 者優異’但是若使高濃度的鍍敷排水通過，則變無法充分 回收貴金屬離子。因此，必須管理自鍍敷洗淨槽排水時的 貴金屬離子濃度。 作爲自以各種濃度含有貴金屬的複數種類之廢液中有 效率地回收貴金屬之方法，例如已知使以低濃度含有貴金 屬的低濃度廢液通過螯合系離子交換樹脂，而將貴金屬吸 附於螯合系離子交換樹脂，取出所吸附的貴金屬，使以高 濃度含有貴金屬的高濃度廢液在電解槽中被電解處理，而 在電極上析出貴金屬，回收所析出的貴金屬之方法（專利 文獻1 )。 [先前技術文獻] [專利文獻] [專利文獻1]特開2001-279343號公報 【發明內容】 -6- 201226632 [發明所欲解決的問題] 以往，作爲自鍍敷回收槽部分地排水之方法，採用使 定期地溢流之方法或藉由計時器來自動設定而定期地排水 之時間管理法、或操作者手動地定期排水之方法。如此地 ，藉由定期地排出一定量的鍍敷回收槽內的收容液，及注 水而定期地減低鍍敷回收槽內的收容液之貴金屬離子濃度 0 然而，鍍敷回收槽內的收容液之貴金屬離子濃度，未 必經常以一定的比例上升，視情況而定，也會急劇地上升 。又，按照鍍敷被處理物的生產量，鍍敷回收槽內的收容 液之貴金屬離子濃度係有各式各樣的變動。因此，於含有 比較低濃度的貴金屬離子之鍍敷排水時，得不到充分的電 流密度，藉由電解回收法來回收貴金屬離子的效率變差。 另一方面，於含有比較高濃度的貴金屬離子之鍍敷排水時 ，以自動設定的循環時間會無法處理，此係成爲使貴金屬 離子的回收效率降低之原因。 再者，鍍敷回收槽內的收容液之貴金屬離子濃度若過 度上升，則來自後步驟的處理槽之鍍敷洗淨槽的鏟敷排水 中所含有的貴金屬離子濃度上升，藉由樹脂回收法、活性 碳吸附回收法來回收貴金屬離子係有變無法充分進行之問 題。 本發明之目的在於提供一種方法，其可自鍍敷回收槽 及鍍敷洗淨槽所排出之含有貴金屬離子的鍍敷排水中高效 率地回收貴金屬離子，而且可抑制鍍敷被處理物的性能不 201226632 良。 [解決問題的手段] 本發明者爲了解決上述問題，進行專心致力硏究，結 果發現將鍍敷回收槽及鑛敷洗淨槽內的收容液之貴金屬離 子濃度維持在指定的範圍者，以該知識爲基礎，終於完成 本發明。即，本發明係自鍍敷排水回收貴金屬離子之方法 ，其係藉由使來自鍍敷回收槽的每一次之排水量成爲鍍敷 回收槽的滿水量之10〜5 0%的範圍內，而且於鎪敷回收槽 內，成爲確保鍍敷被處理物的浸漬之量，而將鍍敷回收槽 內的收容液之貴金屬離子濃度以高濃度維持在一定的範圍 ’而且將鍍敷洗淨槽內的收容液之貴金屬離子濃度以低濃 度維持在一定的範圍。 於本發明中，可對於貴金屬離子的濃度以高濃度維持 在一定的範圍之來自鍍敷回收槽的鍍敷排水，倂用電解回 收法與樹脂回收法或活性碳吸附回收法來回收貴金屬離子 ’對於貴金屬離子的濃度以低濃度維持在一定的範圍之來 自鍍敷洗淨槽的鍍敷排水，藉由樹脂回收法或活性碳吸附 回收法來回收貴金屬離子。 [發明的效果] 若依照本發明，可在不停止鍍敷被處理物的鍍敷處理 下，自鍍敷回收槽及鍍敷洗淨槽所排出之含有貴金屬離子 的鍍敷排水中高效率地回收貴金屬離子，而且可抑制鍍敷 -8 - 201226632 被處理物的性能不良。 【實施方式】 [實施發明的形態] ‘ 本發明係適用於一般的鍍敷處理，即含有以下步驟之 處理：在收容有鍍敷液的鍍敷槽中浸漬被處理物以進行鑛 敷之步驟，在鍍敷回收槽內的收容液中浸漬被處理物，最 初洗淨被處理物之步驟，及在鍍敷洗淨槽內的收容液中浸 漬被處理物，最終洗淨被處理物之步驟；對於來自鍍敷回 收槽的鍍敷排水，倂用電解回收法與樹脂回收法或活性碳 吸附回收法來回收貴金屬離子，另一方面，對於來自鍍敷 洗淨槽的鍍敷排水，藉由樹脂回收法或活性碳吸附回收法 來回收貴金屬離子。 前述被處理物係如電子零件或印刷配線板等，被一對 的輥所連續鍍敷處理之製品，及於鍍敷槽等中，重複浸漬 、提起步驟，分批地鍍敷處理之製品。又，鍍敷回收槽及 鍍敷洗淨槽內的收容液，通常爲經離子交換樹脂所處理的 離子交換水，但在自鍍敷洗淨槽的收容液中回收貴金屬離 子後，已進行活性碳處理及逆滲透膜處理的純水亦可適用 〇 於本發明中，藉由使來自鍍敷回收槽的每一次之排水 量成爲鍍敷回收槽的滿水量之10〜50%的範圍內，而且於 鍍敷回收槽內，成爲確保鍍敷被處理物的浸漬之量，而將 鍍敷回收槽內的收容液之貴金屬離子濃度以高濃度維持在 -9- 201226632 一定的範圍’而且將鍍敷洗淨槽內的收容液之貴金屬離子 濃度以低濃度維持在一定的範圍。而且，可對於貴金屬離 子的濃度以高濃度維持在一定的範圍之來自鍍敷回收槽的 鍍敷排水’倂用電解回收法與樹脂回收法或活性碳吸附回 收法來回收貴金屬離子，對於貴金屬離子的濃度以低濃度 維持在一定的範圍之來自鍍敷洗淨槽的鍍敷排水，藉由樹 脂回收法或活性碳吸附回收法來回收貴金屬離子。 來自鍍敷回收槽的每一次之排水量較佳爲鍍敷回收槽 的滿水量之10〜50 %的範圍內，而且於鍍敷回收槽內，較 佳成爲確保鍍敷被處理物的浸漬之量。每一次的排水量若 超過鍍敷回收槽的滿水量之5 0 %，則由於注水而使鍍敷回 收槽中的水溫大幅變動，將附著於鍍敷被處理物的過剩之 貴金屬離子或鹽成分回收之效率係降低，更且黴菌或細菌 等變容易繁殖，對鍍敷被處理物的附著而導致性能不良， 或良率降低。 另一方面，每一次的排水量若低於滿水量之1 0 %，則 貴金屬離子濃度的管理、及鍍敷回收槽的排水、注水作業 變煩雜。又，由於作業的煩雜而發生管理不良，將附著於 鍍敷被處理物的過剩之貴金屬離子或鹽成分回收之效率係 降低，不僅污染鍍敷被處理物，而且貴金屬離子的回收效 率亦會降低。再者，使每一次的排水量成爲確保鍍敷被處 理物的浸漬之量的理由，係爲了不停止鍍敷處理。 又，鍍敷回收槽內的收容液之水溫較佳爲3 5°C以上， 更佳爲40°C以上。鏟敷回收槽未必需要進行積極的溫度調201226632 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for recovering precious metal ions from mineral deposits, particularly for high efficiency recovery in plating drainage from a plating recovery tank and a plating cleaning tank. A method of recovering precious metal ions by self-adhesive drainage of noble metal ions and suppressing poor performance of a plated material to be treated. [Prior Art] A precious metal is an industrially very useful material because it is excellent in physical properties, reliability, and aesthetics. As a plating material, it is used in a wide range of fields including electronic components such as electronic components and printed wiring boards. use. On the other hand, precious metals are scarcely present and are very expensive materials. Therefore, it is required to recover and reuse the precious metal contained in the plating drainage as much as possible. Similarly, the plating drainage system is divided into drainage from the plating tank, the plating recovery tank, and the sputum washing tank. Since the plating recovery tank functions as a primary cleaning tank after the plating treatment of the plating tank, the drainage water from the plating recovery tank contains noble metal ions having a lower concentration than the drainage of the plating tank. Further, since the plating cleaning tank functions as a secondary or tertiary cleaning tank, the drain water from the plating cleaning tank contains noble metal ions having a lower concentration than the drainage water in the plating recovery tank. Thus, the concentration of precious metal ions of the ore drainage discharged from each tank is different. Further, it is required to wash out the precious metal ions or salt components excessively attached to the mineral-coated material in the plating recovery tank and the plating washing tank, and to suppress the organic matter of the components of the plating solution of the plating -5 - 201226632 The occurrence of mold or bacteria, and the management of the plating tank. As a method for recovering precious metal ions from the plating drainage, an electrolytic recovery method, a resin recovery method, and an activated carbon adsorption recovery method are generally known. The electrolytic recovery method is excellent for recovering precious metal ions from plating drainage having a high concentration of noble metal ions. However, if the plating is drained at a low concentration, the current density does not rise even if the electrolytic cell is circulated, and the noble metal ions are not increased. The recycling efficiency is worse. On the other hand, the resin recovery method and the activated carbon adsorption recovery method are excellent in recovering precious metal ions from plating drainage having a low concentration of noble metal ions. However, if a high concentration of plating drainage is passed, the precious metal ions cannot be sufficiently recovered. . Therefore, it is necessary to manage the concentration of precious metal ions when draining from the plating bath. As a method for efficiently recovering a noble metal from a plurality of kinds of waste liquids containing precious metals in various concentrations, for example, it is known that a low-concentration waste liquid containing a noble metal at a low concentration is passed through a chelate-type ion exchange resin, and a noble metal is adsorbed to the chelate. A method of extracting a noble metal adsorbed by a high-concentration waste liquid containing a noble metal at a high concentration in a electrolytic cell, and depositing a precious metal on the electrode to recover the deposited precious metal (Patent Document 1) . [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2001-279343 (Summary of the Invention) -6-201226632 [Problem to be Solved by the Invention] Conventionally, a method of partially draining water from a plating recovery tank A method of periodically draining the method of periodically overflowing or automatically setting by a timer, or a method of manually draining the water manually by the operator. In this manner, by periodically discharging a predetermined amount of the liquid in the plating recovery tank and injecting water, the precious metal ion concentration of the liquid in the plating recovery tank is periodically reduced by 0. However, the liquid in the plating tank is poured. The concentration of precious metal ions does not always increase at a certain rate, and may rise sharply depending on the situation. Further, according to the production amount of the plated material to be treated, the concentration of the noble metal ions in the solution liquid in the plating recovery tank varies widely. Therefore, when plating drainage containing a relatively low concentration of noble metal ions, a sufficient current density cannot be obtained, and the efficiency of recovering noble metal ions by the electrolytic recovery method is deteriorated. On the other hand, in the case of plating drainage containing a relatively high concentration of noble metal ions, the cycle time which is automatically set cannot be handled, which is a cause of lowering the recovery efficiency of noble metal ions. When the concentration of the noble metal ions of the liquid in the plating tank is excessively increased, the concentration of precious metal ions contained in the slag drainage water from the plating tank of the treatment tank in the subsequent step is increased by the resin recovery method. The activated carbon adsorption recovery method recovers the problem that the noble metal ion system cannot be sufficiently changed. An object of the present invention is to provide a method for efficiently recovering precious metal ions from a plating drainage bath containing precious metal ions discharged from a plating recovery tank and a plating cleaning tank, and suppressing the performance of the plating material to be processed. 201226632 Good. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have focused their efforts on the above-mentioned problems, and as a result, it has been found that the concentration of precious metal ions in the plating liquid in the plating recovery tank and the mineral cleaning tank is maintained within a specified range. Based on knowledge, the present invention has finally been completed. That is, the present invention is a method for recovering precious metal ions from a plating drainage by making the amount of water discharged from the plating recovery tank into a range of 10 to 50% of the total amount of water in the plating recovery tank, and In the argon recovery tank, the amount of the impregnation of the material to be treated is ensured, and the concentration of the noble metal ions of the contained liquid in the plating recovery tank is maintained at a high concentration in a high concentration, and the plating is cleaned in the tank. The concentration of noble metal ions in the contained liquid is maintained at a low concentration in a certain range. In the present invention, the plating drainage from the plating recovery tank can be maintained at a high concentration in the concentration of the noble metal ions, and the noble metal ions can be recovered by the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method. The noble metal ions are recovered by a resin recovery method or an activated carbon adsorption recovery method for the plating drainage from the plating cleaning tank in which the concentration of the noble metal ions is maintained at a low concentration. [Effects of the Invention] According to the present invention, it is possible to efficiently recover the plated drainage water containing precious metal ions discharged from the plating recovery tank and the plating cleaning tank without stopping the plating treatment of the material to be processed. Precious metal ions, and can inhibit plating -8 - 201226632 The performance of the treated object is poor. [Embodiment] [Embodiment of the Invention] The present invention is applied to a general plating treatment, that is, a treatment comprising the steps of immersing a workpiece in a plating tank containing a plating solution for mineralization. a step of immersing the object to be treated in the liquid in the plating tank, first washing the object to be treated, and immersing the object in the liquid in the plating tank, and finally washing the object to be treated For the plating drainage from the plating recovery tank, the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method are used to recover the precious metal ions, and on the other hand, the plating drainage from the plating cleaning tank is used. The resin recovery method or the activated carbon adsorption recovery method recovers precious metal ions. The object to be treated is a product which is continuously plated by a pair of rolls, such as an electronic component or a printed wiring board, and is subjected to repeated immersion and lifting steps in a plating bath or the like, and the processed product is plated in batches. Further, the plating solution in the plating recovery tank and the plating washing tank is usually ion-exchanged water treated with an ion exchange resin, but is activated after recovering precious metal ions from the liquid containing the plating bath. The pure water treated by the carbon treatment and the reverse osmosis membrane may also be suitable for use in the present invention, wherein the amount of water discharged from the plating recovery tank is within a range of 10 to 50% of the total amount of water in the plating recovery tank, and In the plating recovery tank, the amount of the impregnation of the material to be treated is ensured, and the concentration of the noble metal ions of the liquid in the plating recovery tank is maintained at a high concentration in the range of -9-201226632 and is plated. The noble metal ion concentration of the contained liquid in the washing tank is maintained at a low concentration in a certain range. Further, it is possible to recover precious metal ions by using an electrolytic recovery method and a resin recovery method or an activated carbon adsorption recovery method for the plating drainage from the plating recovery tank in which the concentration of the noble metal ions is maintained at a high concentration in a high concentration, for the noble metal ions. The concentration is maintained at a low concentration in a plating bath from the plating bath, and the precious metal ions are recovered by a resin recovery method or an activated carbon adsorption recovery method. The amount of water discharged from the plating recovery tank is preferably in the range of 10 to 50% of the total amount of water in the plating recovery tank, and in the plating recovery tank, it is preferable to ensure the amount of impregnation of the plating material to be treated. . When the amount of water per drain exceeds 50% of the amount of water in the plating recovery tank, the water temperature in the plating recovery tank greatly changes due to water injection, and excess precious metal ions or salt components adhering to the material to be treated are deposited. The efficiency of recovery is lowered, and molds, bacteria, and the like are easily propagated, and adhesion to the plated material is poor, resulting in poor performance or a decrease in yield. On the other hand, if the displacement per time is less than 10% of the full water amount, the management of the precious metal ion concentration and the drainage and water injection operation of the plating recovery tank become complicated. In addition, management troubles occur due to troublesome work, and the efficiency of recovering excess precious metal ions or salt components adhering to the material to be plated is reduced, which not only contaminates the material to be treated, but also reduces the recovery efficiency of precious metal ions. . Further, the reason why the amount of water discharged per time is the amount of impregnation for ensuring the plating of the workpiece is to prevent the plating treatment from being stopped. Further, the water temperature of the liquid contained in the plating recovery tank is preferably 35 ° C or higher, more preferably 40 ° C or higher. Shovel coating recovery tank does not necessarily require positive temperature adjustment
-10- 201226632 整，但較佳爲尤其不使水溫過度降低。特別地，若水溫低 於3 5°C，則附著於鍍敷被處理物的過剩之貴金屬離子或鹽 成分的洗出效率變差，變成促進黴菌或細菌等的繁殖，由 於對於鍍敷被處理物，貴金屬離子或鹽成分殘留或黴菌或 細菌附著，而引起性能不良及良率降低。 一般地於鍍敷槽中，在60〜90 °C左右的加溫狀態下施 予鍍敷處理。因此，經加溫的鍍敷被處理物及附著於鍍敷 被處理物的鍍敷液，係在鍍敷回收槽中移動，而成爲使鍍 敷回收槽的水溫上升之原因。另一個使鍍敷回收槽的水溫 上升之原因，係因爲連續設置鍍敷槽及鍍敷回收槽，由來 自鍍敷槽的輻射熱所造成。 然而，水溫上升未必會導致鍍敷回收槽中的鍍敷被處 理物之性能不良或良率降低。當然，如前述記載，鍍敷回 收槽內的收容液之水溫較佳爲3 5 °C以上，更佳爲4(TC以上 ，特別地，從附著於鍍敷被處理物的過剩之貴金屬離子或 鹽成分的洗出效率良好，抑制黴菌或細菌的繁殖之觀點來 看，水溫高者係較佳。 一般地，當鍍敷被處理物的處理量少時，於以往的時 間管理法或溢流法及全量替換法中，過剩地進行排水及注 水，而成爲引起水溫降低之原因。 因此，於本發明中，如後述地，重要的是在鍍敷回收 槽內設置電極’藉由電流値及經由校正曲線來估計貴金屬 離子濃度，而估計鍍敷被處理物的處理量，使來自鍍敷回 收槽的每一次之排水量成爲鍍敷回收槽的滿水量之10〜-10- 201226632 Integrity, but it is better not to excessively reduce the water temperature. In particular, when the water temperature is lower than 35 ° C, the elution efficiency of excess precious metal ions or salt components adhering to the material to be treated is deteriorated, and the growth of molds, bacteria, and the like is promoted, and the plating is treated. Residues of precious metal ions or salt components or mold or bacteria adhesion, resulting in poor performance and reduced yield. Generally, plating treatment is applied to the plating bath at a heating state of about 60 to 90 °C. Therefore, the plated material to be treated which has been heated and the plating solution adhering to the plated material are moved in the plating recovery tank, which causes the water temperature in the plating recovery tank to rise. Another reason for the increase in the temperature of the water in the plating recovery tank is that the plating bath and the plating recovery tank are continuously provided, which is caused by the radiant heat from the plating tank. However, an increase in the temperature of the water does not necessarily result in poor performance or a decrease in yield of the plating treatment in the plating recovery tank. As a matter of course, as described above, the water temperature of the liquid contained in the plating recovery tank is preferably 35 ° C or higher, more preferably 4 (TC or more, in particular, from excess precious metal ions attached to the plated material to be treated. Or the salt component is excellent in washing efficiency, and it is preferable to suppress the growth of mold or bacteria. Generally, when the amount of the treated material to be treated is small, the conventional time management method or In the overflow method and the full-scale replacement method, drainage and water injection are excessively performed, which causes a decrease in water temperature. Therefore, in the present invention, as will be described later, it is important to provide an electrode in the plating recovery tank. The current 値 and the concentration of the precious metal ions are estimated through the calibration curve, and the amount of the treated material to be treated is estimated, so that the amount of water discharged from the plating recovery tank becomes the full amount of water in the plating recovery tank.
-11 - 201226632 50%的範圍之量。例如，藉由熱量計 水溫50°C時，以20°C的注水置換滿水 成爲降低1 〇°C的範圍，即使鍍敷被處 時，也不使水溫低於3 5 °C而管理。 於本發明中，將鍍敷回收槽內的 濃度以高濃度維持在指定的範圍。以 圍的排水，係適合倂用電解回收法與 吸附回收法。 此處所謂以高濃度維持在一定的 鎪敷洗淨槽內的收容液之貴金屬離子 —定的範圍者比較下，以高濃度維持 又，於貴金屬離子的回收之設備 離子濃度或每單位時間的處理量，適 的設置個數或樹脂及活性碳的塡充量 發明的貴金屬離子回收方法，即使來 鍍敷回收槽的鍍敷排水，只要含有相 可在一個途徑中收集各自的鍍敷排水 作爲本發明的實施形態，當貴金 適宜選擇倂用電解回收法與樹脂回收 法者，另一方面，當低濃度時，適宜 性碳吸附回收法。 爲了以高效率電解回收槽內的收 當投入回收設備時，較佳爲將貴金屬 的範圍。於一般的電解回收法中，按 算，當鍍敷回收槽的 量的50%時，水溫係 理物的處理量比較少 收容液之貴金屬離子 高濃度維持在一定範 樹脂回收法或活性碳 範圍，就是意味與將 濃度以低濃度維持在 者。 設計中，按照貴金屬 宜選擇電解回收裝置 等。再者，若使用本 自並列設置的複數之 同的貴金屬離子，則 ，進行電解回收。 屬離子爲高濃度時， 法或活性碳吸附回收 選擇樹脂回收法或活 容液之貴金屬離子， 離子濃度維持在一定 照鍍敷裝置之排水時 -12- 201226632 的貴金屬離子濃度或排水的每單位時間之處理量，設計電 解回收裝置的設置個數等回收設備。將來自鍍敷回收槽所 排出的收容液一次儲存，自該儲存槽，將一定的處理量移 動到電解回收用槽，一邊使收容液在電解回收用槽與電解 回收裝置循環，一邊電解回收貴金屬離子。電解回收係藉 由循環時間來設定，對於貴金屬離子濃度的變動，適宜地 調整循環時間。因此，所謂一定的範圍，就是維持在適合 於設計貴金屬離子的回收設備之處理性能的濃度，若超過 一定的範圍，則變成超過電解回收後的樹脂或活性碳吸附 回收之回收可能容量，回收效率降低。另一方面，若低於 一定的範圍，則在電解回收中，低濃度的回收效率低，每 單位時間的回收效率降低。 根據以上，將收容液的貴金屬離子濃度以高濃度維持 在一定的範圍者，係可最大限度地利用回收設備的回收效 率，結果可實現高收率。 又，於來自鍍敷回收槽的收容液中，取決於鍍敷液的 種類，會有電流密度無法充分上升的情況，爲了電流密度 的上升，亦可任意地追加添加苛性鈉等的電解質。 例如，當將本發明所規定之鍍敷回收槽內的收容液之 貴金屬離子以高濃度維持在一定的範圍時，較佳爲以10〜 20 0mg/L的範圍維持。鍍敷回收槽內的收容液之貴金屬離 子的濃度若超過200mg/L，則即使併用電解回收法與樹脂 回收法或活性碳吸附回收法，貴金屬離子的回收也不充分 ，而且由於過剩的貴金屬離子流出到鍍敷洗淨槽，鍍敷洗 -13- 201226632 淨槽的貴金屬離子濃度超過1 0mg/L的可能性變高，而降低 來自鍍敷洗淨槽的鍍敷排水中所含有的貴金屬離子之回收 效率。 另一方面’鍍敷回收槽內的收容液之貴金屬離子濃度 若未達1 0mg/L ’則電解回收法與樹脂回收法或活性碳吸附 回收法之倂用係成爲過剩的設計，變成經濟上無效率。又 ，鍍敷回收槽內的收容液中所含有的貴金屬離子之濃度低 於10mg/L的管理，在實施形態上係幾乎沒有，不符合現實 〇 於本發明中，鍍敷洗淨槽內的收容液之貴金屬濃度， 係藉由在鍍敷回收槽中將貴金屬離子濃度維持在一定的濃 度範圍，而將由鍍敷回收槽移動至鍍敷洗淨槽的貴金屬離 子以低濃度維持在一定的範圍。又，鍍敷回收槽內的收容 液經由電解回收法所處理後之收容液，亦同樣地被以低濃 度維持在一定的範圍。由於任一者皆可以低濃度被維持在 一定的範圍，可依照貴金屬離子濃度及每單位時間的處理 量來適宜選擇樹脂及活性碳的塡充量等。 例如，當將本發明所規定之鍍敷洗淨槽內的收容液之 貴金屬濃度以低濃度維持在一定的範圍時，較佳爲維持在 1 Omg/L以下。此係因爲若超過1 Omg/L，則藉由樹脂回收法 或活性碳吸附回收法來回收貴金屬離子會變不充分。 如前述，鍍敷回收槽內的收容液之貴金屬離子濃度最 大爲200mg/L，因此，附著於自鍍敷回收槽所送出的鍍敷 被處理物之過剩的貴金屬離子之最大濃度爲200mg/L，例-11 - 201226632 The amount of 50% range. For example, when the water temperature is 50 ° C by calorimeter, the replacement of the full water with water injection at 20 ° C becomes a range of 1 〇 ° C reduction, and the water temperature is not lower than 35 ° C even when the plating is applied. management. In the present invention, the concentration in the plating recovery tank is maintained at a high concentration in a specified range. The drainage is suitable for electrolytic recovery and adsorption recovery. Here, in the range of the precious metal ions of the contained liquid which is maintained at a high concentration in a fixed bathing bath, the ion concentration of the device is maintained at a high concentration, and the ion concentration of the precious metal ions is recovered or per unit time. The amount of the treatment, the appropriate number of the resin or the charge of the activated carbon, the precious metal ion recovery method of the invention, even if the plating drainage of the plating recovery tank is included, as long as the phase is contained, the respective plating drainage can be collected in one way. In the embodiment of the present invention, when the precious gold is appropriately selected, the electrolytic recovery method and the resin recovery method are used, and on the other hand, when the concentration is low, the carbon adsorption recovery method is suitable. In order to efficiently charge the recovery tank in the recovery tank into a recovery apparatus, it is preferable to limit the range of the precious metal. In the general electrolytic recovery method, when the amount of the plating recovery tank is 50%, the treatment amount of the water temperature treatment material is relatively small, and the high concentration of the noble metal ions of the storage liquid is maintained at a certain resin recovery method or activated carbon. The range means that the concentration is maintained at a low concentration. In the design, an electrolytic recovery unit should be selected according to the precious metal. Further, if a plurality of the same noble metal ions which are arranged in parallel are used, electrolytic recovery is carried out. When the genus ion is at a high concentration, the method or activated carbon adsorption recovery selects the precious metal ion of the resin recovery method or the living solution, and the ion concentration is maintained at a precious metal ion concentration of the -12-201226632 or the drainage per unit of the drainage of the plating apparatus. The processing capacity of time, designing the number of sets of electrolytic recovery devices and other recycling equipment. The storage liquid discharged from the plating recovery tank is once stored, and a certain amount of treatment is moved from the storage tank to the electrolytic recovery tank, and the storage liquid is circulated in the electrolytic recovery tank and the electrolytic recovery unit, and the precious metal is electrolytically recovered. ion. The electrolysis recovery is set by the cycle time, and the cycle time is appropriately adjusted for the variation of the concentration of the noble metal ions. Therefore, the so-called range is to maintain the concentration of the processing performance of the recovery equipment suitable for designing precious metal ions. If it exceeds a certain range, it will exceed the recovery capacity of the resin or activated carbon adsorption recovery after electrolysis recovery, and the recovery efficiency. reduce. On the other hand, if it is less than a certain range, in the electrolytic recovery, the recovery efficiency of the low concentration is low, and the recovery efficiency per unit time is lowered. According to the above, when the concentration of the noble metal ions of the contained liquid is maintained at a high concentration in a certain range, the recovery efficiency of the recovery equipment can be utilized to the utmost, and as a result, a high yield can be achieved. In addition, the current density may not be sufficiently increased depending on the type of the plating solution in the liquid to be contained in the plating recovery tank, and an electrolyte such as caustic soda may be arbitrarily added in order to increase the current density. For example, when the noble metal ions of the contained liquid in the plating recovery tank defined by the present invention are maintained at a high concentration in a certain range, it is preferably maintained in the range of 10 to 20 mg/L. When the concentration of the noble metal ions in the storage liquid in the plating recovery tank exceeds 200 mg/L, the recovery of the noble metal ions is insufficient even if the electrolytic recovery method, the resin recovery method, or the activated carbon adsorption recovery method are used in combination, and the excess noble metal ions are excessive. Flow out to the plating bath, plating wash-13-201226632 The possibility of the precious metal ion concentration of the clean tank exceeding 10 mg/L becomes high, and the precious metal ions contained in the plating drain from the plating bath are reduced. Recovery efficiency. On the other hand, if the concentration of noble metal ions in the liquid in the plating recovery tank is less than 10 mg/L, the use of the electrolytic recovery method, the resin recovery method, or the activated carbon adsorption recovery method becomes an excessive design and becomes economically no efficiency. Moreover, the management of the concentration of the noble metal ions contained in the storage liquid in the plating recovery tank is less than 10 mg/L, and there is almost no embodiment, which is not in accordance with the present invention, and is in the plating cleaning tank. The precious metal concentration of the contained liquid is maintained at a certain concentration range by maintaining the concentration of the noble metal ions in the plating recovery tank to a certain concentration range, thereby maintaining the precious metal ions moved from the plating recovery tank to the plating cleaning tank at a low concentration. . Further, the contained liquid in the plating recovery tank treated with the electrolytic recovery method is similarly maintained at a low concentration in a predetermined range. Since either of them can be maintained at a low concentration in a certain range, the amount of charge of the resin and activated carbon can be appropriately selected in accordance with the concentration of the noble metal ions and the amount of treatment per unit time. For example, when the concentration of the noble metal in the receiving liquid in the plating bath defined by the present invention is maintained at a low concentration in a predetermined range, it is preferably maintained at 10 mg/L or less. In this case, if it exceeds 1 Omg/L, recovery of precious metal ions by the resin recovery method or the activated carbon adsorption recovery method may become insufficient. As described above, since the concentration of the noble metal ions in the plating solution in the plating recovery tank is at most 200 mg/L, the maximum concentration of excess precious metal ions adhering to the plated material to be processed from the plating recovery tank is 200 mg/L. ,example
S -14 - 201226632 如在鍍敷洗淨槽中若藉由純水將上述附著液稀釋至25〜50 倍’則25倍稀釋時的貴金屬離子濃度爲8mg/L，50倍稀釋 時爲4mg/L，被維持在1 〇mg/L以下。 於本發明中’當自鍍敷回收槽的鍍敷排水中回收貴金 屬離子時，倂用電解回收法與樹脂回收法或活性碳吸附回 收法而進行。不僅電解回收法單獨，而且藉由與樹脂回收 法或活性碳吸附回收法的組合，可顯著地提高貴金屬離子 的回收效率。 電解回收法係在電解槽中導入鍍敷排水，藉由電分解 使貴金屬離子析出在電極上，進行回收之方法。作爲所使 用的陽極’可例示由Pt鍍敷Ti材、Ir燒結Ti材或肥粒鐵材 所成的電極，作爲陰極，可例示由Ti材、SUS材或肥粒鐵 材所成的電極。於本發明中，作爲自鍍敷回收槽的鍍敷排 水中以高電解效率回收貴金屬的條件，按照鏟敷液的種類 及貴金屬離子種，適宜地設定電極的種類或電流密度。例 如，於氰系鍍敷液的排水中，由於氰離子溶解Pt，故使用 Ir燒結Ti材電極。又，於含有Pt或Pd等的鉛族之鍍敷液的 排水中，因爲藉由水之水解所產生的氫而剝離所析出的鉑 族，故以低電流密度使用。再者，在陰極所析出的貴金屬 之去除、回收方法，係沒有特別的限定，但藉由王水等來 剝離而去除、回收所析出的貴金屬時，宜使用Ti材當作陰 極。 樹脂回收法係使鍍敷排水通過樹脂而捕集貴金屬離子 ，燒掉該樹脂而回收貴金屬之方法。作爲樹脂回收法所用 -15- 201226632 的樹脂’例如可舉出陽離子交換樹脂、陰離子交換樹脂、 螯合樹脂、合成吸附材，較佳爲高效率地回收貴金屬離子 者。具體地，陰離子交換樹脂，例如具有四級銨鹼（三甲 基銨鹼、二甲基乙醇銨鹼等）的強鹼性離子交換樹脂、具 有一級、二級或三級胺基的弱鹼性離子交換樹脂等：陽離 子交換樹脂’例如具有磺酸基的強酸性離子交換樹脂、具 有氟化烷基磺酸基的超強酸性離子交換樹脂、具有羧基、 膦酸基、次膦酸基的弱酸性離子交換樹脂等；螯合樹脂， 例如亞脒基醋酸型螯合樹脂、聚胺型螯合樹脂係合適。 與電解回收法倂用的活性碳吸附回收法，係使用活性 碳捕集貴金屬離子，使此活性碳燃燒而灰化，自所得之灰 化物回收貴金屬離子之方法。使用活性碳捕集貴金屬離子 時’例如於鍍敷排水中含浸活性碳，使鍍敷排水通過在管 柱中所塡充的活性碳而進行。 自鍍敷洗淨槽的鍍敷排水中回收貴金屬離子時，使用 樹脂回收法或括性碳吸附回收法來進行。樹脂回收法或活 性碳吸附回收法係如前述。 使來自鍍敷回收槽的每一次之排水量成爲鍍敷回收槽 的滿水量之1 〇〜5 0%的範圍時，鍍敷回收槽的排水及注水 較佳爲藉由一部分排水、一部分注水而進行。通常，工業 上爲了進行大量的鍍敷處理，要求以不妨礙鍍敷被處理物 的製造之方式，連續地在鍍敷回收槽中處理，但若一次實 施全量排水，則使鍍敷被處理物的鍍敷處理停止，故前置 時間變長，有生產性降低之問題。再者，若進行全量排水 -16- 201226632 而進行新的全量注水，則使鍍敷回收槽的水溫大幅地變動 ，故貴金屬離子的回收效率降低。 作爲使來自鍍敷回收槽的每一次之排水量成爲鍍敷@ 收槽的滿水量之1 〇〜5 0 %的範圍之方法，並沒有特別的限 定，例如於鍍敷回收槽中設置二個電極、使恆定電壓或恆 定電流通電的電源、與使排水和注水作動的電動閥等’對 鍍敷回收槽進行通電，藉由所測定的電流値或電位値來控 制排水及注水的電動閥等之作動。 具體地，例如在設置於鍍敷回收槽的電極間，以恆定 電壓或恆定電流進行通電，對於鍍敷回收槽內的收容液， 預先作成表示電流値或電位値、與該收容液內所含有的貴 金屬離子濃度之關係的校正曲線，在設置於鍍敷回收槽的 電極間，以恆定電壓或恆定電流進行通電，測定該電極間 的電流値或電位値，以所得之測定値與上述校正曲線爲基 礎，將鍍敷回收槽內的收容液之貴金屬離子濃度定量，當 所得之定量値達到指定的設定値時，藉由進行鍍敷回收槽 的排水及/或注水，而將鎪敷回收槽內的收容液之貴金屬 離子濃度以高濃度維持在一定的範圍。 作爲前述電極，在陽極中較佳爲由提高電流密度時不 溶出的Pt鍍敷Ti材、Ir燒結Ti材或肥粒鐵材所成之電極， 在陰極中較佳爲由Ti材、SUS材或肥粒鐵材所成之電極。 又’該電極的形狀可適宜選擇平板、圓棒、圓筒、網狀等 ，但若考慮安裝時的電極相向，更佳爲圓棒或圓筒的形狀 -17- 201226632 於作成前述校正曲線時，及實際上對鍍敷回收槽進行 通電，測定電流値或電位値時，關於設置於鍍敷回收槽的 電極之電極形狀、電極長度、電極間距離及外加電壓，係 配合鍍敷回收槽的鍍敷排水之電導度而適宜選擇。該鍍敷 排水的電導度係包含貴金屬離子及其它電解質等的鍍敷排 水全體之電導度，若貴金屬離子濃度高，則電導度變高。 當鍍敷排水的貴金屬離子濃度-電流値曲線的斜率大時， 爲比較低的電壓施加，電極直徑小，可縮短電極，取得寬 的電極間距離。另一方面，當斜率小時，爲比較高的電壓 施加，電極直徑大，可加長電極，取得寬的電極間距離， 而調整斜率。例如，將外加電壓設定在1 2〜24 V，可使對 應於貴金屬離子濃度的前述上限値之電流値成爲200〜 8 00mA，使對應於貴金屬離子濃度的前述下限値之電流値 成爲100〜5 00mA。較佳爲選擇可將貴金屬離子濃度的前 述上下値與前述下限値的差分値管理在100〜300m A的範 圍之電極條件。 鍍敷回收槽的排水及/或注水，例如採用排水用及注 水用電動閥同時作動之方式，於排水用電動閥作動，排水 完成後，注水用電動閥作動之方式，排水中注水用電動閥 作動之方式等，藉由控制盤自動地控制而進行。再者，代 替電動閥，可使用電磁閥等具有同樣的機能者。 於排水用及注水用電動閥同時作動之方式中，若鍍敷 回收槽內的收容液之電流値到達所設定的上限値，則排水 用及注水用電動閥同時作動，若到達所設定的下限値，則 -18- 201226632 排水用及注水用電動閥停止。藉由鍍敷回收槽內的收容液 的電流値，控制排水及注水的時期，而管理貴金屬離子濃 度的上限値及下限値。 . 於排水用電動閥作動，排水完成後，注水用電動閥作 動之方式中，若鍍敷回收槽內的收容液之電流値到達所設 定的上限値，則僅排水用電動閥作動，排水至下限水位爲 止。此時，該收容液的電流値係沒有變動。若排水完成， 則接著注水用電動閥作動，若注水到達滿水位則停止。藉 由鍍敷回收槽內的收容液之電流値，控制排水的時期，而 管理貴金屬離子溫度的上限値，排水量及注水量係藉由水 位的測定來管理，而管理貴金屬離子濃度的下限値。 於排水中注水用電動閥作動之方式中，若鍍敷回收槽 內的收容液之電流値到達所設定的上限値，則排水用電動 閥作動，在該排水中注水用電動閥作動，若前述電流値到 達所設定的下限値，則排水用及注水用電動閥的作動係停 止，注水係結束。藉由鑛敷回收槽內的收容液的電流値， 控制排水及注水的時期，而管理貴金屬離子濃度的上限値 及下限値。 於本發明中，回收對象的貴金屬離子之貴金屬係Au、 Pd、Ag、Pt或Rh。因此，在鍍敷被處理物所處理的鍍敷液 之種類係含有Au、Pd、Ag、Pt及Rh中的至少一種以上之 鍍敷液，亦可爲含有上述貴金屬與Ni、Co、Fe、Zn等的非 貴金屬之合金鍍敷液。又，作爲鍍敷方法，可舉出氰系鍍 敷、非氰系鍍敷、電解鏟敷、無電解鍍敷等。還有，鍍敷 -19- 201226632 槽內所收容的鍍敷液通常使用貴金屬離子濃度爲1〜7〇g/L 者。 以下，舉出實施本發明時，維持鍍敷回收槽及鑛敷洗 淨槽內的收容液之貴金屬濃度的實施形態之例。 [實施形態1] 使用鍍AU液（日本電鍍工程（EEJA )公司製，商品 名：Temperex MLA100 ; Au6〜10g/L)，進行鍍敷處理之 際，將鍍敷回收槽內的收容液之水溫設定在5 0 °C，將該收 容液的Au離子濃度之上限値設定在50〜5 9m g/L，將下限値 設定在34〜43 mg/L時，作爲設置於鍍敷回收槽的電極、電 極形狀、電極長度、電極間距離及外加電壓之最合適條件 的1例，若外加電壓成爲24V，則顯示Au離子濃度的前述 上限値之電流値爲3 50mA，顯示前述下限値的電流値爲 2 5 0mA，Au離子濃度的前述上限値及前述下限管理値之差 分以電流値表示被管理在l〇〇mA的範圍之最合適電極，係 由Pt鍍敷Ti材所成的陽極，由Ti材所成的陰極，例示圓棒 形狀、電極直徑Φ 15mm、電極長度23mm、極間距離35mm 以排水用及注水用電動閥同時作動之方式來實施鍍敷 回收槽的排水與注水時，當到達前述上限値的350mA時， 排水用及注水用電動閥同時作動，當到達前述下限値的 250mA時，停止排水用及注水用電動閥的作動。因此’所 排水的Au離子濃度係前述上限濃度的50〜59mg/L與前述下 -20- 201226632 限濃度的34〜43m g/L之範圍’鍍敷回收槽內的收容液之 20 %被交換。附著於鏟敷回收槽所洗淨的鍍敷被處理物之 附著液的Au離子濃度係最大59mg/L ’於鍍敷洗淨槽中’藉 由以水稀釋此附著液，而將Au離子濃度維持在10mg/L以下 的低濃度。注水的水溫係約2 〇 °C ’連續運轉中的鍍敷回收 槽之水溫爲44〜46 °C。 來自鎪敷回收槽的鍍敷排水中所含有的高濃度之Au離 子的電解回收，係使用由Ir燒結Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約200L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell)，以 130〜200mA/dm2的電解密度進行Au離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Au離子之樹脂回收，係各自可使用同樣 的樹脂’使用塡充有陰離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Au離子的回 收。 本實施形態的回收處理後之殘留的Au離子濃度係未達 0.2 m g/ L 〇 [實施形態2] 使用鍍Au液（EEJA公司製，商品名：Temperex 8400 ;Au3〜5g/L ) ’進行鍍敷處理之際，將鍍敷回收槽內的 收容液之水溫設定在50°C，將該收容液的Au離子濃度之上 限値設定在50〜63mg/L，將下限値設定在33〜42mg/L時， •21 - 201226632 作爲設置於鍍敷回收槽的電極、電極形狀、電極長度、電 極間距離及外加電壓之最合適條件的1例，若外加電壓成 爲24V，則顯示Au離子濃度的前述上限値之電流値爲 370mA，顯示前述下限値的電流値爲270mA，Au離子濃度 的前述上限値及前述下限管理値之差分以電流値表示被管 理在100m A的範圍之最合適電極，係由Pt鍍敷Ti材所成的 陽極，由Ti材所成的陰極，例示圓棒形狀、電極直徑φ 15mm、電極長度23mm、極間距離35mm。 與實施形態1同樣地，以排水用及注水用電動閥同時 作動之方式來實施鍍敷回收槽的排水與注水時，當到達前 述上限値的3 70m A時，排水用及注水用電動閥同時作動， 當到達前述下限値的2 70mA時，停止排水用及注水用電動 閥的作動。因此，所排水的Au離子濃度係前述上限濃度的 50〜63mg/L與前述下限濃度的33〜42mg/L之範圍，鏟敷回 收槽內的收容液之2 0 %被交換。附著於鍍敷回收槽所洗淨 的鍍敷被處理物之附著液的Au離子濃度係最大63 mg/L ’於 鍍敷洗淨槽中，藉由以水稀釋此附著液’而將^離子濃度 維持在10mg/L以下的低濃度。注水的水溫係約20°C ’連續 運轉中的鍍敷回收槽之水溫爲44〜46 °C。 來自鍍敷回收槽的鍍敷排水中所含有的高濃度之△11離 子的電解回收，係使用由Ir燒結Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約200L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell )，以 130〜200mA/dm2的電解密度進行Au離子的回收。S -14 - 201226632 If the above-mentioned adherent is diluted to 25 to 50 times by pure water in the plating bath, the precious metal ion concentration at 25-fold dilution is 8 mg/L, and at 50-fold dilution, 4 mg/L. L is maintained below 1 〇 mg/L. In the present invention, when the noble metal ions are recovered from the plating drainage of the plating recovery tank, the ruthenium is carried out by an electrolytic recovery method, a resin recovery method or an activated carbon adsorption recovery method. Not only the electrolytic recovery method alone, but also a combination of a resin recovery method or an activated carbon adsorption recovery method can remarkably improve the recovery efficiency of noble metal ions. The electrolytic recovery method is a method in which a plating drainage is introduced into an electrolytic cell, and precious metal ions are deposited on the electrode by electrolysis. An electrode formed of a Pt-plated Ti material, an Ir-sintered Ti material, or a fat-grained iron material can be exemplified as the anode, and an electrode made of a Ti material, a SUS material, or a fat-grained iron material can be exemplified as the cathode. In the present invention, as the conditions for recovering the noble metal by high electrolysis efficiency in the plating drainage water from the plating recovery tank, the type or current density of the electrode is appropriately set in accordance with the type of the shovel liquid and the noble metal ion species. For example, in the drainage of the cyanide plating solution, since the cyanide ions dissolve Pt, the Ti sintered Ti material electrode is used. Further, in the drainage of the plating liquid of the lead group containing Pt or Pd or the like, since the precipitated platinum group is peeled off by hydrogen generated by hydrolysis of water, it is used at a low current density. In addition, the method of removing and recovering the precious metal deposited on the cathode is not particularly limited. However, when the precipitated noble metal is removed by the aqua regia or the like, the Ti material is preferably used as the cathode. The resin recovery method is a method in which a plating drainage is passed through a resin to collect precious metal ions, and the resin is burned to recover a precious metal. The resin used in the resin recovery method -15-201226632 includes, for example, a cation exchange resin, an anion exchange resin, a chelating resin, and a synthetic adsorbent, and it is preferred to recover precious metal ions with high efficiency. Specifically, an anion exchange resin such as a strongly basic ion exchange resin having a quaternary ammonium base (trimethylammonium base, dimethylethanolammonium base, etc.) or a weakly basic one having a primary, secondary or tertiary amine group Ion exchange resin or the like: a cation exchange resin' such as a strongly acidic ion exchange resin having a sulfonic acid group, a super strong acidic ion exchange resin having a fluorinated alkyl sulfonic acid group, and a weak group having a carboxyl group, a phosphonic acid group, and a phosphinic acid group. An acidic ion exchange resin or the like; a chelate resin such as a mercaptoacetic acid type chelate resin or a polyamine type chelate resin is suitable. The activated carbon adsorption recovery method used in the electrolytic recovery method is a method in which noble metal ions are collected by using activated carbon to burn and ash the activated carbon, and precious metal ions are recovered from the obtained ash. When the noble metal ions are trapped using activated carbon, for example, the plating water is impregnated with activated carbon, and the plating drainage is carried out by the activated carbon charged in the column. When precious metal ions are recovered from the plating drainage of the plating washing tank, the resin recovery method or the carbon adsorption recovery method is used. The resin recovery method or the activated carbon adsorption recovery method is as described above. When the amount of water discharged from the plating recovery tank is in the range of 1 〇 to 50% of the total amount of water in the plating recovery tank, the drainage and water injection in the plating recovery tank are preferably performed by a part of the drainage and a part of the water injection. . In general, in order to perform a large amount of plating treatment in the industry, it is required to continuously treat the material to be processed in the plating recovery tank so as not to hinder the production of the material to be plated. However, if the entire amount of drainage is performed once, the material to be treated is plated. Since the plating treatment is stopped, the lead time is prolonged, and the productivity is lowered. In addition, when a full amount of water is poured in the range of -16 to 201226632, the water temperature in the plating recovery tank is largely changed, so that the recovery efficiency of precious metal ions is lowered. The method of setting the amount of water discharged from the plating recovery tank to the range of 1 〇 to 50% of the total amount of water in the plating @ sink is not particularly limited. For example, two electrodes are provided in the plating recovery tank. A power supply that energizes a constant voltage or a constant current, an electric valve that operates the drain and the water injection, and the like, and an electric valve that controls the drainage and water injection by the current or the potential 値 measured. Actuate. Specifically, for example, electricity is supplied between the electrodes provided in the plating recovery tank at a constant voltage or a constant current, and the liquid contained in the plating recovery tank is previously formed to indicate current 値 or potential 値 and contained in the accommodating liquid. The calibration curve of the relationship between the concentration of the noble metal ions is energized at a constant voltage or a constant current between the electrodes provided in the plating recovery tank, and the current 値 or potential 値 between the electrodes is measured to obtain the measured enthalpy and the above calibration curve. Based on the basis, the precious metal ion concentration of the receiving liquid in the plating recovery tank is quantified, and when the obtained quantitative enthalpy reaches the specified setting enthalpy, the draining and/or water injection of the plating recovery tank is performed, and the sputum recovery tank is used. The concentration of noble metal ions in the contained liquid is maintained at a high concentration in a certain range. As the electrode, an electrode formed of a Pt-plated Ti material, an Ir-sintered Ti material, or a ferrite-grained iron material which is not eluted when the current density is increased is preferably used in the anode, and the cathode material is preferably made of a Ti material or a SUS material. Or the electrode made of fat iron. Further, the shape of the electrode may be selected from a flat plate, a round bar, a cylinder, a mesh, etc., but in consideration of the electrode orientation at the time of mounting, it is more preferably a shape of a round bar or a cylinder -17-201226632 when the calibration curve is prepared. And actually, when the plating recovery tank is energized and the current 値 or potential 値 is measured, the electrode shape, the electrode length, the distance between the electrodes, and the applied voltage of the electrode provided in the plating recovery tank are matched with the plating recovery tank. The conductivity of the plating drainage is suitable for selection. The electrical conductivity of the plating drainage includes the electrical conductivity of the entire plating drainage of precious metal ions and other electrolytes, and if the concentration of the noble metal ions is high, the electrical conductivity becomes high. When the slope of the noble metal ion concentration-current 値 curve of the plating drainage is large, the electrode diameter is small for a relatively low voltage application, and the electrode can be shortened to obtain a wide interelectrode distance. On the other hand, when the slope is small, for a relatively high voltage application, the electrode diameter is large, the electrode can be lengthened, a wide interelectrode distance is obtained, and the slope is adjusted. For example, when the applied voltage is set to 1 2 to 24 V, the current 値 corresponding to the upper limit 贵 of the noble metal ion concentration can be made 200 to 800 mA, and the current 値 corresponding to the lower limit 贵 of the noble metal ion concentration becomes 100 to 5 00mA. It is preferable to select an electrode condition in which the difference 前 between the upper and lower 値 and the lower limit 贵 of the noble metal ion concentration can be managed in the range of 100 to 300 m A . Drainage and/or water injection in the plating recovery tank. For example, the electric valve for drainage and water injection is operated simultaneously, and the electric valve for drainage is actuated. After the drainage is completed, the electric valve for water injection is actuated, and the electric valve for water injection in the drainage is used. The manner of actuation, etc., is performed by the control panel being automatically controlled. Further, in place of the electric valve, a solenoid valve or the like having the same function can be used. In the method of simultaneously operating the electric valve for drainage and water injection, if the current 値 of the liquid contained in the plating recovery tank reaches the set upper limit 値, the electric valve for drainage and water injection is simultaneously actuated, and the lower limit is reached.値, -18- 201226632 The electric valve for draining and water injection is stopped. The upper limit 値 and the lower limit 贵 of the precious metal ion concentration are managed by controlling the current of the liquid in the recovery tank to control the period of drainage and water injection. When the electric valve is operated by the electric valve for draining, and the electric valve for the water injection is activated, if the current 値 of the liquid in the plating tank reaches the set upper limit 仅, only the electric valve for draining is actuated, and the water is drained to The lower limit water level. At this time, the current of the contained liquid did not change. If the drainage is completed, the water injection is then actuated by the electric valve, and if the water injection reaches the full water level, it stops. By controlling the current of the liquid in the storage tank, the period of drainage is controlled, and the upper limit of the temperature of the precious metal ions is managed. The displacement and the amount of water are managed by the measurement of the water level, and the lower limit of the concentration of the precious metal ions is managed. In the method of operating the electric water valve for water injection in the drainage, if the current 値 of the liquid contained in the plating recovery tank reaches the set upper limit 値, the electric valve for drainage is actuated, and the water injection is actuated by the electric valve in the drain. When the current 値 reaches the set lower limit 値, the actuation of the electric valve for drainage and water injection is stopped, and the water injection system is completed. The upper limit 値 and the lower limit 贵 of the precious metal ion concentration are managed by the current 値 of the contained liquid in the mineral recovery tank to control the period of drainage and water injection. In the present invention, the precious metal of the noble metal ion of the object to be recovered is Au, Pd, Ag, Pt or Rh. Therefore, the type of the plating solution to be treated by plating the workpiece is a plating solution containing at least one of Au, Pd, Ag, Pt, and Rh, and may contain the noble metal and Ni, Co, Fe, An alloy plating solution of non-noble metal such as Zn. Further, examples of the plating method include cyanide plating, non-cyanide plating, electrolytic shovel, and electroless plating. Also, plating -19- 201226632 The plating solution contained in the tank is usually a noble metal ion concentration of 1 to 7 〇g/L. Hereinafter, an example of an embodiment in which the concentration of the noble metal in the plating liquid in the plating recovery tank and the mineral cleaning tank is maintained in the practice of the present invention will be described. [Embodiment 1] When the plating treatment is performed using a plating AU solution (manufactured by EIJA Co., Ltd., trade name: Temperex MLA100; Au6 to 10 g/L), the water of the liquid in the plating tank is recovered. When the temperature is set to 50 ° C, the upper limit A of the Au ion concentration of the contained solution is set to 50 to 5 9 m g / L, and the lower limit 値 is set to 34 to 43 mg / L, as the plating storage tank is provided. In the case of the most suitable conditions for the electrode, the electrode shape, the electrode length, the distance between the electrodes, and the applied voltage, if the applied voltage is 24 V, the current 値 of the upper limit A of the Au ion concentration is 3 50 mA, and the current of the lower limit 値 is displayed.値 is 250 mA, the difference between the upper limit A of the Au ion concentration and the lower limit management 以 is the most suitable electrode to be managed in the range of 10 mA by the current ,, and is an anode formed by Pt plating Ti material. The cathode formed of the Ti material is exemplified by a round bar shape, an electrode diameter of 15 mm, an electrode length of 23 mm, and an interelectrode distance of 35 mm. When the drainage and the water injection electric valve are simultaneously operated to perform drainage and water injection in the plating recovery tank, When reaching the aforementioned upper limit 値 35 At 0 mA, the electric valve for draining and water injection is operated at the same time, and when it reaches 250 mA of the lower limit 値, the operation of the electric valve for draining and water injection is stopped. Therefore, the concentration of the Au ion to be drained is 50 to 59 mg/L of the upper limit concentration, and the range of the lower limit of the range of 34 to 43 m g/L of the lower -20-201226632 is exchanged. 20% of the contained liquid in the plating recovery tank is exchanged. . The Au ion concentration of the plating solution adhered to the slag-coated recovery tank is up to 59 mg/L in the plating bath. In the plating bath, the concentration of Au ions is diluted by water. Maintain a low concentration below 10 mg/L. The water temperature of the water injection is about 2 〇 °C. The water temperature in the plating recovery tank during continuous operation is 44 to 46 °C. The electrolytic recovery of the high-concentration Au ions contained in the plating drainage from the sputum recovery tank is a cycle treatment capacity of about 200 L using an anode made of an Ir sintered Ti material and a cathode electrode made of a Ti material. The electrolysis recovery device (manufactured by Tanaka Kiyoshi Metal Co., Ltd.: MINI Recover Cell) was used to recover Au ions at an electrolytic density of 130 to 200 mA/dm 2 . The resin from the low-concentration Au ion contained in the plating liquid of the waste liquid after the electrolytic recovery and the plating washing tank is recovered, and the same resin can be used. The ion exchange resin device using the anion exchange resin is used. (Tianzhong Precious Metal Industry Co., Ltd.: Eagle RE) to recover Au ions. The Au ion concentration remaining after the recovery treatment in the present embodiment is less than 0.2 mg/L. [Embodiment 2] Plating Au liquid (trade name: Temperex 8400; Au3 to 5 g/L, manufactured by EEJA Co., Ltd.) is used for plating. At the time of the application, the water temperature of the liquid contained in the plating recovery tank is set to 50 ° C, the upper limit A of the Au ion concentration of the contained liquid is set to 50 to 63 mg / L, and the lower limit 値 is set to 33 to 42 mg. /L, • 21 - 201226632 As an example of the most suitable conditions for the electrode, electrode shape, electrode length, distance between electrodes, and applied voltage to be placed in the plating recovery tank, if the applied voltage is 24V, the Au ion concentration is displayed. The current 値 of the upper limit 値 is 370 mA, and the current 値 showing the lower limit 値 is 270 mA, and the difference between the upper limit 値 of the Au ion concentration and the lower limit management 以 represents the most suitable electrode in the range of 100 m A by the current ,. The anode formed of the Pt-plated Ti material and the cathode formed of the Ti material are exemplified by a round bar shape, an electrode diameter of 15 mm, an electrode length of 23 mm, and an interelectrode distance of 35 mm. In the same manner as in the first embodiment, when the drainage and the water injection electric valve are simultaneously operated to perform the drainage and water injection of the plating recovery tank, when the water temperature reaches 3 70 m A of the upper limit ,, the electric valve for drainage and water injection is simultaneously When the operation reaches 2 70 mA of the lower limit 値, the operation of the electric valve for drainage and water injection is stopped. Therefore, the Au ion concentration to be drained is in the range of 50 to 63 mg/L of the upper limit concentration and 33 to 42 mg/L of the lower limit concentration, and 20% of the contained liquid in the shovel returning tank is exchanged. The Au ion concentration of the plating solution adhering to the plating material to be cleaned by the plating recovery tank is 63 mg/L at the maximum in the plating bath, and the ion is diluted by water. The concentration is maintained at a low concentration of 10 mg/L or less. The water temperature of the water injection is about 20 ° C. The water temperature of the plating recovery tank during continuous operation is 44 to 46 ° C. The electrolytic recovery of the high concentration of Δ11 ions contained in the plating drainage from the plating recovery tank is performed by using an anode formed of an Ir sintered Ti material and a cathode electrode formed of a Ti material. A 200 L electrolytic recovery device (manufactured by Tanaka Kiyoshi Metal Co., Ltd.: MINI Recover Cell) was used to recover Au ions at an electrolytic density of 130 to 200 mA/dm 2 .
-22- 201226632 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Au離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有陰離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Au離子的回 收。 本實施形態的回收處理後之殘留的Au離子濃度係未達 0 · 2mg/L 〇 [實施形態3] 使用鍍Au液（EEJA公司製，商品名：Autrobond TN ;Aul〜3g/L)，進行鍍敷處理之際，將鍍敷回收槽內的 收容液之水溫設定在50°C，將該收容液的Au離子濃度之上 限値設定在28〜95mg/L，將下限値設定在17〜74mg/L時， 作爲設置於鍍敷回收槽的電極、電極形狀、電極長度、電 極間距離及外加電壓之最合適條件的1例，若外加電壓成 爲1 2 V，則顯示Au離子濃度的前述上限値之電流値爲 450mA，顯示前述下限値的電流値爲3 50mA，作爲Au離子 濃度的前述上限値及前述下限管理値之差分以電流値表示 被管理在100m A的範圍之最合適電極，係由Pt鍍敷Ti材所 成的陽極，由Ti材所成的陰極，例示圓棒形狀、電極直徑 φ 15mm、電極長度23mm、極間距離35mm。 與實施形態1同樣地，以排水用及注水用電動閥同時 作動之方式來實施鍍敷回收槽的排水與注水時，當到達前 述上限値的45 0mA時，排水用及注水用電動閥同時作動， -23- 201226632 當到達前述下限値的3 50mA時，停止排水用及注水用電動 閥的作動》因此，所排水的Au離子濃度係前述上限濃度的 28〜95mg/L與前述下限濃度的17〜74mg/L之範圍，鍍敷回 收槽內的收容液之20%被交換。附著於銨敷回收槽所洗淨 的鍍敷被處理物之附著液的Au離子濃度係最大95mg/L，於 鍍敷洗淨槽中，藉由以水稀釋此附著液，而將Au離子濃度 維持在l〇mg/L以下的低濃度。注水的水溫係約20°C，連續 運轉中的鍍敷回收槽之水溫爲44〜46°C » 來自鍍敷回收槽的鍍敷排水中所含有的高濃度之人11離 子的電解回收，係使用由Ir燒結Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約2 00 L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell)，以 130〜200mA/dm2的電解密度進行Au離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Au離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有陰離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Au離子的回 收。 本實施形態的回收處理後之殘留的Au離子濃度係未達 0_2mg/L。 [實施形態4] 使用鍍Pd液（EEJA公司製，商品名：Palladex 100; Pd25〜3 0g/L)，進行鍍敷處理之際，將鍍敷回收槽內的 201226632 收容液之水溫設定在50 °C，將該收容液的Pd離子之上限値 設定在129〜157mg/L，將下限値設定在38〜77mg/L時，作 爲設置於鍍敷回收槽的電極、電極形狀、電極長度、電極 間距離及外加電壓之最合適條件的1例，若外加電壓成爲 12V，則顯示Pd離子濃度的前述上限値之電流値爲550mA ，顯示前述下限値的電流値爲450mA，Pd離子濃度的前述 上限値及前述下限管理値之差分以電流値表示被管理在 100mA的範圍之最合適電極，係由Pt鍍敷Ti材所成的陽極 ，由Ti材所成的陰極電極，例示圓棒形狀、電極直徑φ 15mm、電極長度23mm、極間距離45mm。 以排水用電動閥作動，排水完成後，注水用電動閥作 動之方式，實施鍍敷回收槽的排水與注水時，當到達前述 上限値的55 0mA時，排水用電動閥作動，當排出滿水量的 40%時，注水用電動閥作動，當滿水時停止。因此，所排 水的Pd離子濃度係前述上限濃度的129〜157mg/L之範圍， 附著於鍍敷回收槽所洗淨的鍍敷被處理物之附著液的Pd離 子濃度係最大157mg/L，於鍍敷洗淨槽中，藉由以水稀釋 此附著液，而將Pd離子濃度維持在10mg/L以下的低濃度。 注水的水溫係約20 °C，連續運轉中的鍍敷回收槽之水溫爲 4 0 〜4 2。(： ° 來自鍍敷回收槽的鍍敷排水中所含有的高濃度之Pd離 子的電解回收，係使用由Pt鍍敷Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約2 00L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell)，以 -25- 201226632 100〜270mA/dm2的電解密度進行Pd離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Pd離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有螯合樹脂的離子交換樹脂裝置（田中 貴金屬工業公司製：Eagle RE )來進行Pd離子的回收。 本實施形態的回收處理後之殘留的Pd離子濃度係未達 0 · 5 m g/L 〇 [實施形態5] 使用鍍Ag液（NE Chemcat公司製，商品名：AG-10; Ag50〜70 g/L)，進行鎪敷處理之際，將鍍敷回收槽內的 收容液之水溫設定在50 °C，將該收容液的Ag離子濃度之上 限値設定在148〜195mg/L，將下限値設定在49〜83mg/L時 ，作爲設置於鍍敷回收槽的電極、電極形狀、電極長度、 電極間距離及外加電壓之最合適條件的1例，若外加電壓 成爲12V，則顯示Ag離子濃度的前述上限値之電流値爲 6 5 0mA，顯示前述下限値的電流値爲5 50mA，作爲Ag離子 濃度的前述上限値及前述下限管理値之差分以電流値表示 被管理在100m A的範圍之最合適電極，係由Pt鍍敷Ti材所 成的陽極，由Ti材所成的陰極電極，例示圓棒形狀、電極 直徑φ 15mm、電極長度23mm、極間距離55mm。 與實施形態4同樣地，鍍敷回收槽的排水及注水，當 以排水用電動閥作動，排水完成後，注水用電動閥作動之 方式實施時，於到達前述上限値的650mA時，排水用電動-22- 201226632 Recycling of the low-concentration Au ion resin contained in the waste liquid after electrolytic recovery and the plating drainage of the plating washing tank, the same resin can be used, and the anion exchange resin is used. An ion exchange resin device (manufactured by Tanaka Precious Metal Industries Co., Ltd.: Eagle RE) was used to recover Au ions. The concentration of Au ions remaining after the recovery treatment in the present embodiment is less than 0. 2 mg/L. [Embodiment 3] The Au plating solution (trade name: Autrobond TN; Aul to 3 g/L, manufactured by EEJA Co., Ltd.) is used. At the time of the plating treatment, the water temperature of the storage liquid in the plating recovery tank is set to 50 ° C, the upper limit A of the Au ion concentration of the storage liquid is set to 28 to 95 mg/L, and the lower limit 値 is set to 17 to 17 In the case of 74 mg/L, as an example of the most suitable conditions for the electrode, the electrode shape, the electrode length, the distance between the electrodes, and the applied voltage, which are provided in the plating recovery tank, when the applied voltage is 1 2 V, the Au ion concentration is displayed as described above. The current 値 of the upper limit 450 is 450 mA, and the current 値 showing the lower limit 値 is 3 50 mA, and the difference between the upper limit A of the Au ion concentration and the lower limit management 以 represents the most suitable electrode managed in the range of 100 m A by the current ,, The anode formed of Pt-plated Ti material, and the cathode formed of the Ti material, for example, has a round bar shape, an electrode diameter of φ 15 mm, an electrode length of 23 mm, and an interelectrode distance of 35 mm. In the same manner as in the first embodiment, when the drainage and water injection for the drainage and the water injection are simultaneously performed, when the water is discharged to the plating recovery tank and the water is poured, the electric valve for drainage and water injection is simultaneously activated when the temperature reaches 45 0 mA of the upper limit 値. , -23- 201226632 When the 3 50 mA of the lower limit 値 is reached, the operation of the electric valve for draining and water injection is stopped. Therefore, the Au ion concentration to be drained is 28 to 95 mg/L of the upper limit concentration and 17 of the lower limit concentration. In the range of ~74 mg/L, 20% of the receiving liquid in the plating recovery tank is exchanged. The Au ion concentration of the plating solution adhered to the plated material to be treated by the ammonium coating recovery tank is 95 mg/L at the maximum, and the Au concentration is adjusted by diluting the adhering liquid with water in the plating washing tank. Maintain a low concentration below l〇mg/L. The water temperature of the water injection is about 20 ° C, and the water temperature of the plating recovery tank during continuous operation is 44 to 46 ° C. » Electrolytic recovery of high-concentration human 11 ions contained in the plating drainage from the plating recovery tank An electrolytic recovery device (manufactured by Tanaka Kiyoshi Metal Co., Ltd.: MINI Recover Cell) having a cycle processing capacity of about 200 L, which is composed of an anode made of a sintered Ti material and a cathode electrode made of a Ti material, is used. The Au density was recovered at an electrolytic density of 200 mA/dm2. The resin from the low-concentration Au ion contained in the plating liquid of the waste liquid after electrolysis and the plating washing tank is recovered, and the same resin can be used, and an ion exchange resin device filled with an anion exchange resin is used. (Tianzhong Precious Metal Industry Co., Ltd.: Eagle RE) to recover Au ions. The Au ion concentration remaining after the recovery treatment in the present embodiment was less than 0-2 mg/L. [Embodiment 4] When the plating treatment is performed using a Pd-plated solution (trade name: Palladex 100; Pd25 to 30 g/L, manufactured by EEJA Co., Ltd.), the water temperature of the 201226632 containing liquid in the plating recovery tank is set at 50 ° C, the upper limit P of the Pd ion of the contained liquid is set to 129 to 157 mg / L, and the lower limit 値 is set to 38 to 77 mg / L, as the electrode, the electrode shape, the electrode length, and the length of the electrode provided in the plating recovery tank. In the case of the most suitable condition for the distance between the electrodes and the applied voltage, if the applied voltage is 12 V, the current 値 showing the upper limit P of the Pd ion concentration is 550 mA, and the current 値 showing the lower limit 値 is 450 mA, and the Pd ion concentration is as described above. The difference between the upper limit 値 and the lower limit management 以 indicates the most suitable electrode to be managed in the range of 100 mA by the current ,, and is an anode formed of a Pt-plated Ti material, and a cathode electrode formed of a Ti material, exemplified by a round bar shape, The electrode diameter was φ 15 mm, the electrode length was 23 mm, and the interelectrode distance was 45 mm. When the drainage is completed, the water injection is operated by the electric valve, and when the drainage and water injection of the plating recovery tank are performed, when the upper limit 値 is 55 mA, the electric valve for drainage is actuated, and when the water is discharged At 40% of the time, the water injection is actuated by the electric valve and stops when it is full. Therefore, the Pd ion concentration to be drained is in the range of 129 to 157 mg/L of the upper limit concentration, and the Pd ion concentration of the adhering liquid adhered to the plating target treated by the plating recovery tank is at most 157 mg/L. In the plating washing tank, the Pd ion concentration is maintained at a low concentration of 10 mg/L or less by diluting the adhering liquid with water. The water temperature of the water injection is about 20 °C, and the water temperature of the plating recovery tank during continuous operation is 40 to 4 2 . (: ° Electrolytic recovery of high-concentration Pd ions contained in the plating drainage from the plating recovery tank is performed by using an anode formed of Pt-plated Ti material and a cathode electrode made of Ti material. An electrolytic recovery unit (MINI Recover Cell, manufactured by Tanaka Kiyoshi Metal Co., Ltd.) with a capacity of about 200 liters was used to recover Pd ions at an electrolytic density of -25 to 201226632 100 to 270 mA/dm2. The waste liquid and plating after the above electrolytic recovery The resin of the low-concentration Pd ion contained in the plating drainage of the cleaning tank is recovered, and the same resin can be used, and an ion exchange resin device filled with a chelating resin (made by Takahashi Metal Co., Ltd.: Eagle RE) can be used. The Pd ion concentration after the recovery treatment in the present embodiment is less than 0.5 mg/L 实施 [Embodiment 5] The Ag plating solution (manufactured by NE Chemcat, trade name: AG-) is used. 10; Ag50~70 g/L), when the enamel treatment is performed, the water temperature of the liquid contained in the plating recovery tank is set to 50 ° C, and the upper limit Ag of the Ag ion concentration of the contained liquid is set to 148~ 195mg/L, lower limit 値When the temperature is 49 to 83 mg/L, as an optimum condition for the electrode, the electrode shape, the electrode length, the distance between the electrodes, and the applied voltage to be placed in the plating recovery tank, if the applied voltage is 12 V, the Ag ion concentration is displayed. The current 値 of the upper limit 値 is 650 mA, and the current 値 showing the lower limit 値 is 5 50 mA, and the difference between the upper limit Ag of the Ag ion concentration and the lower limit management 以 is represented by the current 値 in the range of 100 m A . The most suitable electrode is an anode formed of a Pt-plated Ti material, and a cathode electrode made of a Ti material, for example, a round bar shape, an electrode diameter of φ 15 mm, an electrode length of 23 mm, and an interelectrode distance of 55 mm. When the drainage and the water injection in the plating recovery tank are operated by the electric valve for drainage, when the water injection is performed by the electric valve after the completion of the drainage, when the water is reached at the upper limit of 650 mA, the electric power for drainage is
-26- 201226632 閥作動，於排出滿水量的5 0 %時，注水用電動閥作動’於 滿水時停止。因此，所排水的Ag離子濃度係前述上限濃度 的148〜195mg/L之範圍，附著妗鍍敷洗淨槽所洗淨的鍍敷 被處理物之附著液的Ag離子濃度係最大195mg/L ’於鍍敷 洗淨槽中，藉由以水稀釋此附著液’而將Ag離子濃度維持 在1 Omg/L以下的低濃度。注水的水溫係約20°C，連續運轉 中的鍍敷回收槽之水溫爲3 9〜4 1°C。 來自鍍敷回收槽的鍍敷排水中所含有的高濃度之Ag離 子的電解回收，係使用由Ir燒結Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約2 〇〇L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell)，以 130〜200mA/dm2的電解密度進行Ag離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鏟敷排水 中所含有的低濃度Ag離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有陰離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Ag離子的回 收。 本實施形態的回收處理後之殘留的Ag離子濃度係未達 0.2mg/L。 [實施形態6] 使用鍍Pt液（EEJA公司製，商品名：Preciousfab PtlOO; PtlO〜I4g/L)，進行鍍敷處理之際，將鍍敷回收 槽內的收容液之水溫設定在50°C，將該收容液的Pt離子濃 -27- 201226632 度之上限値設定在96〜120mg/L，將下限値設定在45〜 63mg/L時，作爲設置於鎪敷回收槽的電極、電極形狀、電 極長度、電極間距離及外加電壓之最合適條件的1例，若 外加電壓成爲1 5 V，則顯示Pt離子濃度的前述上限値之電 流値爲500mA，顯示前述下限値的電流値爲400mA，作爲 Pt離子濃度的前述上限値及前述下限管理値之差分以電流 値表示被管理在l〇〇mA的範圍之最合適電極，係由Pt鍍敷 Ti材所成的陽極，由Ti材所成的陰極電極，例示圓棒形狀 、電極直徑Φ 15mm、電極長度23mm、極間距離40mm。 以排水中注水用電動閥作動之方式來實施鍍敷回收槽 的排水與注水時，當到達前述上限値的500mA時，排水用 電動閥作動，排水中注水用電動閥作動，當到達下限値的 40 0mA時，停止排水用及注水用電動閥之作動。因此，所 排水的Pt離子濃度係前述上限濃度的96〜1 20mg/L與前述 下限濃度的45〜63mg/L之範圍’鍍敷回收槽內的收容液之 40%被交換。附著於鍍敷洗淨槽所洗淨的鍍敷被處理物之 附著液的Pt離子濃度係最大l2〇mg/L，於鍍敷洗淨槽中， 藉由以水稀釋此附著液，而維持在l〇mg/L以下的低濃度。 注水的水溫係約2〇°C，連續運轉中的鍍敷回收槽之水溫爲 4 0 〜4 2。(：。 來自鍍敷回收槽的銨敷排水中所含有的高濃度之Pt離 子的電解回收，係使用由Pt鍍敷Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約2 00L的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell) ’以 -28- 201226632 30〜140m A/dm2的電解密度進行Pt離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Pt離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有陽離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Pt離子的回 收。 本實施形態的回收處理後之殘留的Pt離子濃度係未達 0.5mg/L 〇 [實施形態7] 使用鍍Rh液（NE Chemcat公司製，商品名：RH221 ; Rh3〜5g/L )，進行鍍敷處理之際，將鍍敷回收槽內的收 容液之水溫設定在50 °C，將該收容液的Rh離子濃度之上限 値設定在42〜60mg/L，將下限値設定在16〜32mg/L時，作 爲設置於鍍敷回收槽的電極、電極形狀、電極長度、電極 間距離及外加電壓之最合適條件的1例，若外加電壓成爲 24V，則顯示Rh離子濃度的前述上限値之電流値爲450mA ，顯示前述下限値的電流値爲3 50mA，作爲Rh離子濃度的 前述上限値及前述下限管理値之差分以電流値表示被管理 在100mA的範圍之最合適電極，係由Pt鍍敷Ti材所成的陽 極，由Ti材所成的陰極電極，例示圓棒形狀、電極直徑φ 15mm、電極長度23mm、極間距離35mm。 與實施形態6同樣地，以排水中注水作動之方式來實 施鍍敷回收槽的排水及注水時，當到達前述上限値的 -29 - 201226632 4 5 0m A時，排水電動閥作動，排水中注水用電動閥作動， 當到達前述下限値的350mA時，停止排水用及注水用電動 閥的作動。因此，所排水的Rh離子濃度係前述上限濃度的 42〜60mg/L與前述下限濃度的16〜32mg/L之範圍，鍍敷回 收槽內的收容液之30%被交換。附著於鍍敷洗淨槽所洗淨 的鍍敷被處理物之附著液的Rh離子濃度係最大60mg/L，於 鍍敷洗淨槽中，藉由以水稀釋此附著液，而維持在l〇mg/L 以下的低濃度。注水的水溫係約20°C，連續運轉中的鍍敷 回收槽之水溫爲42〜44°C。 來自鍍敷回收槽的鍍敷排水中所含有的高濃度之Rh離 子的電解回收，係使用由Pt鍍敷Ti材所成的陽極、由Ti材 所成的陰極電極而構成之循環處理容量約2 OOL的電解回收 裝置（田中貴金屬工業公司製：MINI Recover Cell)，以 30〜140mA/dm2的電解密度進行Rh離子的回收。 來自上述電解回收後的廢液及鍍敷洗淨槽的鍍敷排水 中所含有的低濃度Rh離子之樹脂回收，係各自可使用同樣 的樹脂，使用塡充有陽離子交換樹脂的離子交換樹脂裝置 (田中貴金屬工業公司製：Eagle RE)來進行Rh離子的回 收。 本實施形態的回收處理後之殘留的Rh離子濃度係未達 0.5 m g/L。 [比較形態1] 使來自實施形態3的鍍敷回收槽之每一次的排水量成 -30- 201226632 爲鍍敷回收槽的滿水量之而排水，進行收容液的^離 子濃度之上限値及下限値的設定。然而，於6〇%的排水中 ，鍍敷回收槽的水溫係低於3 5 °C，附著於鍍敷被處理物的 過剩之貴金屬離子或鹽成分的洗出效率降低’更且發生徽 菌或細菌的繁殖，發生品質降低所導致的鍍敷被處理物之 良率降低。 [比較形態2 ] 使來自實施形態5的鍍敷回收槽之每一次的排水量成 爲鍍敷回收槽的滿水量之5%而排水’進行收容液的Ag離 子濃度之上限値及下限値的設定。然而，於5%的排水中， 無法在上限値及下限値的範圍中設立充分的差，變無法藉 由Ag離子濃度的電流値進行管理，結果Ag離子濃度超過 800mg/L，將附著於鍍敷被處理物的過剩之貴金屬離子或 鹽成分回收之效率係降低，發生品質降低所導致的鍍敷被 處理物之良率降低。再者，於鍍敷洗淨槽中，Ag離子濃度 係超過離子交換樹脂裝置的回收能力，貴金屬的回收率降 低。 -31 --26- 201226632 The valve is actuated. When the water is discharged at 50% of the full water volume, the water injection is actuated by the electric valve to stop when it is full. Therefore, the Ag ion concentration to be drained is in the range of 148 to 195 mg/L of the above-mentioned upper limit concentration, and the Ag ion concentration of the adhering liquid of the plated workpiece to be washed by the deposition of the ruthenium plating washing tank is 195 mg/L at the maximum. In the plating washing tank, the Ag ion concentration is maintained at a low concentration of 1 Omg/L or less by diluting the adhering liquid with water. The water temperature of the water injection is about 20 ° C, and the water temperature of the plating recovery tank in continuous operation is 3 9 to 4 1 ° C. The electrolytic recovery of the high-concentration Ag ions contained in the plating drainage from the plating recovery tank is a cycle processing capacity of about 2 using an anode made of an Ir sintered Ti material and a cathode electrode made of a Ti material. The electrolytic recovery device of 〇〇L (manufactured by Tanaka Kiyoshi Metal Co., Ltd.: MINI Recover Cell) was used to recover Ag ions at an electrolytic density of 130 to 200 mA/dm 2 . The resin of the low-concentration Ag ion contained in the waste liquid after the electrolysis recovery and the slag drainage of the plating washing tank is recovered, and the same resin can be used, and an ion exchange resin device filled with an anion exchange resin is used. (Tianzhong Precious Metal Industry Co., Ltd.: Eagle RE) to recover Ag ions. The Ag ion concentration remaining after the recovery treatment in the present embodiment was less than 0.2 mg/L. [Embodiment 6] When the plating treatment is performed using a Pt plating solution (trade name: Preciousfab PtlOO; PtlO to I4g/L, manufactured by EEJA Co., Ltd.), the water temperature of the storage liquid in the plating recovery tank is set to 50°. C. The upper limit P of the Pt ion concentration -27-201226632 degree of the contained liquid is set to 96 to 120 mg/L, and the lower limit 値 is set to 45 to 63 mg/L, and the electrode and the electrode shape are provided in the 锼 回收 recovery tank. In the case of the optimum conditions of the electrode length, the distance between the electrodes, and the applied voltage, if the applied voltage is 15 V, the current 値 of the upper limit P of the Pt ion concentration is 500 mA, and the current 値 of the lower limit 値 is 400 mA. The difference between the upper limit 値 of the Pt ion concentration and the lower limit management 以 indicates the most suitable electrode to be managed in the range of 10 mA by the current ,, and is an anode formed of Pt-plated Ti material, and is made of Ti material. The resulting cathode electrode is exemplified by a round bar shape, an electrode diameter of 15 mm, an electrode length of 23 mm, and an interelectrode distance of 40 mm. When the drainage and water injection of the plating recovery tank are performed by the electric valve for water injection in the drainage, when the upper limit 値 500 mA is reached, the electric valve for drainage is actuated, and the water injection in the drainage is actuated by the electric valve, and when the lower limit is reached, At 40 mA, the operation of the electric valve for draining and water injection is stopped. Therefore, the Pt ion concentration to be drained is exchanged between 96 to 1 20 mg/L of the upper limit concentration and 45 to 63 mg/L of the lower limit concentration in the plating recovery tank. The Pt ion concentration of the plating solution adhered to the plating solution to be washed is up to l2 〇 mg/L, and is maintained in the plating washing tank by diluting the adhering liquid with water. Low concentration below l〇mg/L. The water temperature of the water injection is about 2 〇 ° C, and the water temperature of the plating recovery tank during continuous operation is 40 to 4 2 . (: The electrolytic recovery of high-concentration Pt ions contained in the ammonium-coated drainage water from the plating recovery tank is a cycle formed by using an anode formed of a Pt-plated Ti material and a cathode electrode made of a Ti material. Electrolytic recovery unit (MINI Recover Cell, manufactured by Tanaka Kiyoshi Metal Co., Ltd.) with a capacity of approximately 200 liters. 'Pt ions were recovered at an electrolytic density of -28-201226632 30 to 140 m A/dm2. The waste liquid from the above electrolysis recovery and The resin of the low-concentration Pt ion contained in the plating drainage of the plating washing tank is used, and the same resin can be used, and an ion exchange resin device filled with a cation exchange resin is used (Taizhong Precious Metal Industry Co., Ltd.: Eagle RE) The Pt ion concentration after the recovery treatment in the present embodiment is less than 0.5 mg/L 实施 [Embodiment 7] The Rh-plated solution (manufactured by NE Chemcat, trade name: RH221; Rh3) is used. 〜5g/L), when the plating treatment is performed, the water temperature of the storage liquid in the plating recovery tank is set to 50 ° C, and the upper limit R of the Rh ion concentration of the storage liquid is set to 42 to 60 mg/L. Lower limit 値In the case of 16 to 32 mg/L, as an optimum condition for the electrode, the electrode shape, the electrode length, the distance between the electrodes, and the applied voltage to be placed in the plating recovery tank, if the applied voltage is 24 V, the Rh ion concentration is displayed. The current limit 値 of the upper limit 値 is 450 mA, and the current 値 showing the lower limit 値 is 3 50 mA, and the difference between the upper limit R of the Rh ion concentration and the lower limit management 以 represents the most suitable electrode managed in the range of 100 mA by the current 値An anode formed of a Pt-plated Ti material, and a cathode electrode made of a Ti material, for example, a round bar shape, an electrode diameter of φ 15 mm, an electrode length of 23 mm, and an interelectrode distance of 35 mm. In the same manner as in the sixth embodiment, drainage is performed. When the water injection operation is carried out to discharge and fill the plating recovery tank, when the upper limit 値 -29 - 201226632 4 5 0 m A is reached, the drain electric valve is actuated, and the water injection in the drainage is actuated by the electric valve, when reaching the lower limit When 350 mA is used, the operation of the electric valve for draining and water injection is stopped. Therefore, the concentration of Rh ion to be drained is 42 to 60 mg/L of the upper limit concentration and 16 of the lower limit concentration. In the range of 32 mg/L, 30% of the contained liquid in the plating recovery tank is exchanged. The Rh ion concentration of the plating solution adhered to the plating treatment tank is 60 mg/L at the maximum. In the plating cleaning tank, the adhesion liquid is diluted with water to maintain a low concentration of 10 〇 mg/L or less. The water temperature of the water injection is about 20 ° C, and the water temperature of the plating recovery tank during continuous operation 42 to 44 ° C. Electrolytic recovery of high-concentration Rh ions contained in the plating drainage from the plating recovery tank is performed by using an anode formed of Pt-plated Ti material and a cathode electrode formed of Ti material. On the other hand, an electrolytic recovery apparatus (MINI Recover Cell, manufactured by Tanaka Kiyoshi Metal Co., Ltd.) having a circulating treatment capacity of about 2 OOL was used, and Rh ions were recovered at an electrolytic density of 30 to 140 mA/dm 2 . The resin of the low-concentration Rh ion contained in the plating liquid of the waste liquid after the electrolytic recovery and the plating washing tank is recovered, and the same resin can be used, and an ion exchange resin device filled with a cation exchange resin is used. (Tianzhong Precious Metal Industry Co., Ltd.: Eagle RE) to recover Rh ions. The Rh ion concentration remaining after the recovery treatment in the present embodiment is less than 0.5 m g/L. [Comparative Example 1] The amount of water discharged from the plating recovery tank of the third embodiment is -30-201226632, and the water is drained to the full amount of the plating recovery tank, and the upper limit and lower limit of the ion concentration of the storage liquid are performed. Settings. However, in 6% of the drainage, the water temperature of the plating recovery tank is lower than 35 ° C, and the elution efficiency of the excess precious metal ions or salt components attached to the plated material is lowered. The growth of bacteria or bacteria causes a decrease in the yield of the plated material to be treated due to a decrease in quality. [Comparative Example 2] The amount of water discharged from the plating recovery tank of the fifth embodiment is set to 5% of the full water amount of the plating recovery tank, and the drainage is set to the upper limit 値 and the lower limit Ag of the Ag ion concentration of the storage liquid. However, in 5% of the drainage, it is impossible to set a sufficient difference in the range of the upper limit and the lower limit, and it cannot be managed by the current of the Ag ion concentration. As a result, the Ag ion concentration exceeds 800 mg/L, and it adheres to the plating. The efficiency of recovering excess precious metal ions or salt components of the material to be treated is lowered, and the yield of the plated material to be treated is lowered due to a decrease in quality. Further, in the plating bath, the Ag ion concentration exceeds the recovery capacity of the ion exchange resin device, and the recovery rate of the precious metal is lowered. -31 -