46 93 0 4 A7 _ B7 五、發明說明（/) 【發明領域] 本發明係關於一種不溶性陽極鍍銅的方法，更特定而 言’係關於一種以印刷電路板(PCB)工廠回收銅鹽溶液所 製備之氫氧化銅，來補充不溶性陽極鏟銅系統中銅離子之 不溶性陽極鍍銅的方法。 【發明背景] 目前已知的鍍銅系統’根據銅供應方式可分爲溶解性 陽極鍍銅與不溶性陽極鍍銅兩大類。 在傳統的溶解性陽極鍍銅系統中，如圖1所示，因電 鍍時銅在陰極120析出速率與陽極110銅溶出速率不同， 爲避免無法控制鍍浴銅濃度，一般多使用大陽極小陰極方 式操作。同時鍍件120因電流密度及被鍍面積不同，造成 同樣槽體100設計卻無法有相同陰極電流輸出。故一般多 以鈦籃11〇放置磷銅球ill再外包陽極袋m方式做爲溶 解性陽極，一方面易於補充銅，另一方面也易得到大陽極 面積。但由於磷銅球111面積會隨溶解而逐漸縮小，陽極 袋II2無法有效濾除溶解銅之銅泥，以及陽極袋112會吸 脫附光澤劑之故，所以此系統在鍍銅上存在許多藥液穩定 性及潔淨度上之問題。 而在不溶性陽極鍍銅系統(如圖2所示），則可免除藥 液穩定性及潔淨度上之困擾。主要原因在於其銅的供應係 在電鍍槽200外，藥液易於藉過濾達到潔淨度，而且銅濃 度由分析方式添加，更容易得到藥液穩定性。不溶性陽極 <請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -袭·-------訂---------線 ----------------------------- 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） ΐ 4 6 9 3 0 4 A7 — B7 五、發明說明（ 210使用氧化銥或白金，其電力線穩定，也有助於鍍銅均 勻性，如圖3比較兩鍍銅系統的電力線150、250分布。 同時光澤劑只需顧慮於陽極210氧化的消耗，藥液穩定性 更高。 ， 傳統溶解性陽極之鍍銅方法因其銅的來源成本低，也 不需額外電力用於銅溶解，故除非爲特殊或高品質產品， 一般不使用不溶性陽極之鍍銅方法。但隨著電子產品輕薄 短小的趨勢，所以不溶性陽極鍍銅系統未來將日益增多。 進一步考量不溶性陽極的鍍銅方法，現存於市場上有 關此方法所用銅的供應可分爲三種： 1. 以電解方式溶銅，並配合離子交換膜阻隔銅於溶銅 槽中析出。此系統副作用較多，詳列於下： (1) 因銅離子無法100%濾除，沉積於陰極的少量銅成 粉狀存在，造成廢棄物產生。 (2) 離子交換膜壽命不長，且系統易因密封不良而毀 損此隔膜，造成維護保養成本大幅增加。 (3) 光澤劑仍會受電解消耗，藥液成本增高許多。 2. 通入氧氣、臭氧或三價鐵這類氧化物方式溶銅： 此方法優點在於無金屬雜質共同析鍍的問題，同時銅 的來源成本也較低。其主要問題來自於光澤劑，如光澤劑 選用不當，則極易被氧化破壞而造成光澤劑大量損耗，同 時破壞後的裂解產物亦可能造成銅的品質劣化 3. 加入陰離子易移除之銅鹽，如氧化銅（CuO)或碳酸 銅(CuC03)，做爲銅的補充方式。此方法對光澤劑影響小 ------：-------_1 (請先閲讀背面之注意事項再填寫本頁) 幻· --線. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 297公爱） 經濟部智慧財產局員工消費合作社印製 ^693 04 A7 _____ B7 五、發明說明（>) 且維護成本低，但仍有副作用，主要問題如下： (1) 外購銅鹽製作時經常使用回收銅，故難以控制其 金屬雜質，如Zn、Fe、Pb、Ni等，此類雜質會共同析出 影響銅層組織，或累積後影響鍍液中硫酸根的平衡。 (2) 外購銅鹽成本高，特別是高純度者（較溶解性陽極 鍍銅系統所使用之銅來源高40〜90%" 另外考慮銅鹽（如硫酸銅、氯化銅等)水溶液的性質， 其在pH大於7.9之鹼性環境下極易生成氫氧化銅沉澱。 氫氧化銅不溶於水，但可溶於酸性環境下β而在pH小於 13之鹼性環境下，銅溶解度亦可控制於ppm等級。此氫 氧化銅加入鍍銅液會與硫酸反應生成硫酸銅供電鍍用，其 副產品只有水。相較於碳酸銅會有部分碳酸殘存需打氣驅 趕，以及氧化銅溶解度較差而言，氫氧化銅做爲不溶性陽 極之鍍銅方法的銅供應來源較具優勢。 傳統製作氧化銅、氫氧化銅或碳酸銅的流程中，經常 使用回收銅做爲原料，但由於回收銅來源過於複雜’經常 有Ni、Cr、Pb、Zn、Fe等金屬雜質，而此類雜質會在電 鍍時共同析出，影響銅層組織(如形成銅瘤、抗拉性降低) 。而在高階產品時，Pb共析會造成α粒子，影響1C品質 。反觀PCB廠經常有大量含銅廢液’傳統常以硫酸銅形 式回收。由於PCB廠原料種類較單純’回收銅鹽中不易 含其他金屬雜質，以此製作之銅鹽極適合電鍍使用’但仍 需避免陰離子累積的問題。 5 本紙張尺度適用中國國家標準（CNS)A4規格（·21〇 X 297公爱） I !!1! 3'波！ — 訂! — ！-線—--------I ---I I I I----- ν'- - 、.'·-' (請先閱讀背面之注意事項再填寫本頁) 4 6 9304 五、發明說明（f) 【發明目的與槪述】 (請先閱讀背面之注ί項再填寫本頁) 據此，本發明的目的是要提供一種改良的不溶性陽極 鍍銅方法，其可避免上述習知技術所帶來的缺點，以加速 不溶性陽極系統取代傳統溶解性陽極系統之可能性。 本發明係以另一種回收之氫氧化銅來取代傳統製程中 的碳酸銅及氧化銅，做爲不溶性陽極鍍銅系統之銅補充來 源，而達到上述的目的。不僅可大幅降低傳統之碳酸銅及 氧化銅回收製程中的金屬雜質，減少其造成的銅瘤或抗拉 性降低等問題，也可大幅降低不溶性陽極鍍銅之原料成本 ，兼具資源回收的功效。 .根據本發明的方法，採用一不溶性陽極的鍍銅系統， 當中有一溶銅槽，做爲補充銅離子的來源，其可接收來自 鍍銅槽的含銅電解質，根據當中銅離子濃度而補充銅後送 回鍍銅槽。此方法的特徵在於溶銅槽中補充銅離子的來源 係回收之氫氧化銅，其回收製備的過程包括：將PCB廠回 收之銅鹽水溶液加到鹼液中，當pH値控制在8~13時生成 大量不溶於水之沉澱物，所得沉澱物用水洗移除殘留其中 的水溶性鹽類，烘乾後即得氫氧化銅粉末。 ' 經濟部智慧財產局員工消費合作社印製 【圖式之簡單說明】 圖1爲溶解性陽極鑛銅系統市思圖。 圖2爲不溶性陽極鍍銅系統7ft意圖β 圖3爲溶解性及不溶性陽極之電力線分布的比較。 6 本纸張尺度適用中國國家標準（CNS)A4規格（210 x297公釐） 經濟部智慧財產局員工消費合作社印製 46 93 0 4 A7 B7 五、發明說明（y) 【圖式參考符號說明】 100 鍍銅槽 110 陽極鈦籃 111 磷銅球 112 陽極袋 113 陽極導桿 120 陰極鍍件 150 電力線 200 鍍銅槽 210 不溶性陽極 211 ' 陽極導板 220 陰極鍍件 230 銅濃度偵測器 240 溶銅槽 250 電力線 【發明之詳細說明】 根據本發明的不溶性陽極鍍銅方法，其包括：提供一 鍍銅槽200，當中有不溶性陽極210、做爲陰極的鍍件220 與含銅電解質；提供一銅濃度偵測器230，以偵測鍍銅槽 中銅離子的濃度；提供一溶銅槽240，做爲補充銅離子的 來源，其可接收來自鍍銅槽200的含銅電解質，根據當中 銅離子濃度而補充銅後送回鍍銅槽200 ;於陰、陽極之間 施加一有效電壓，以使含銅電解質中的銅析出於鍍件220 上。此方法的特徵在於溶銅槽240中補充銅離子的來源係 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） — — — — — — 1 — 117- ^^ i! 1! 1 訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 469304 A7 __B7______ 五、發明說明（^；) 回收之氫氧化銅，其回收製備的過程包括：將PCB廠回收 之銅鹽水溶液加到鹼液中，當pH値控制在8〜13時生成大 量不溶於水之沉澱物，所得沉澱物用水洗移除殘留其中的 水溶性鹽類，供乾後即得氫氧化銅粉末。 本發明方法的基本架構類似習用的不溶性陽極鍍銅方 法和系統，例如圖2所示，乃此類技藝人士所熟知，故其 操作方式在此不再贅述。而關於本發明的改良與特點所在 ，即以回收之氫氧化銅補充銅離子，其回收製備的過程說 明如下： 將PCB廠回收之銅鹽溶入水中成銅鹽水溶液，或例 如直接取用鍍銅液做爲銅鹽水溶液，直接加到經精確計算 濃度之鹼液中，當pH値控制在8〜13時即可生成大量不 溶於水之氫氧化銅沉澱。所得氫氧化銅沉澱可用水洗移除 殘留其中的水溶性鹽類，烘乾後即可使用。 所使用之鹼液以鋰、鈉、鉀之氫氧化物的水溶液爲佳 ，原因爲一般PCB廠回收之銅鹽多爲硫酸鹽、氯化物或 硝酸鹽，而鋰、鈉、鉀與之化合所生成之鹽類均極容易溶 於水，故生成之鹽類可用較多量之水移除。 由於銅鹽水溶液添加速度及攪拌會影響其中氧化銅共 析比例，而烘乾溫度亦會影響氧化銅生成比例。氧化銅占 氬氧化銅的比例會影響溶解速度，故此比例宜盡可能降低 。舉例而言，銅鹽水溶液添加速度不宜太快，且最好持續 攪拌鹼液。氫氧化銅沉澱物的烘烤溫度例如最好介於 70〜110°C之間，以減少氧化銅的生成機率。 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I II I I---1 名！訂！！線 /! ... 一 (請先閲讀背面之注意事項再見寫本頁) 4693 04 A7 B7 五、發明說明（γ) 而氫氧銅沉澱後之濾淸液pH値宜控制於8〜13範 圍內，以避免過濾後的廢液及水洗液中有過量銅離子累積 ，也有利環保。 另一種製備方法可使用鋰、鈉、鉀之碳酸鹽的鹼液取 代氫氧化物的鹼液，所生成沉澱爲碳酸銅（含結晶水），再 以較高溫烘烤’例如200〜25(TC之間，可將其中二氧化碳 趕出而形成氫氧化銅，並減少碳酸殘存。如果使用鋰、鈉 、鉀之碳酸鹽水溶液，只需過量添加即可控制後續水洗液 中銅離子的帶出量- 本發明中的溶銅槽240基本功能與習知者相同，即做 爲補充銅離子的來源，其可接收來自鍍銅槽200的含銅電 解質，並配合銅濃度偵測器230的自動取樣分析而進行前 述所得的氫氧化銅添加，再把含銅電解質送回鍍銅槽200 。當然，含銅電解質可於流經溶銅槽240的過程中加以過 濾，以保持藥液的潔淨度。此外，不溶性陽極鍍銅系統亦 可搭配一鍍液緩衝系統(未顯示於圖2)，有助於鍍銅系統之 穩定。 下面示範三種氫氧化銅的回收製備過程： 節例1 鍍銅液50升，其成分爲：硫酸銅75克/升，硫酸.200克 /升，氯含量35ppm，光澤劑若干。 鹼液50升，其成分爲：氫氧化鈉200克/升 製備方式：持續攪拌鹼液，並以1:1之體積比例添加鍍銅 9 — — — —— —--— II I I (請先閱讀背面之注意事項再填寫本頁〕46 93 0 4 A7 _ B7 V. Description of the Invention (/) [Field of the Invention] The present invention relates to an insoluble anode copper plating method, and more specifically, it relates to a copper salt solution recovered by a printed circuit board (PCB) factory. The prepared copper hydroxide is used to supplement the insoluble anode copper plating method of copper ions in the insoluble anode copper shovel system. [Background of the Invention] Currently known copper plating systems' can be divided into two categories: soluble anode copper plating and insoluble anode copper plating according to the copper supply mode. In the traditional dissolving anode copper plating system, as shown in Fig. 1, the precipitation rate of copper at the cathode 120 is different from that of the anode 110 during electroplating. In order to avoid the copper concentration in the plating bath cannot be controlled, large anodes and small cathodes are generally used Way operation. At the same time, due to the different current density and plated area of the plated part 120, the same cathode body 100 design cannot have the same cathode current output. Therefore, in general, the phosphor basket is placed in the titanium basket 11 and then the anode bag m is used as the soluble anode. On the one hand, it is easy to supplement copper, and on the other hand, it is easy to obtain a large anode area. However, because the area of the phosphor copper ball 111 will gradually decrease with the dissolution, the anode bag II2 cannot effectively filter the copper sludge that dissolves copper, and the anode bag 112 absorbs and desorbs the gloss agent. Therefore, there are many drugs on the copper plating of this system. Problems in fluid stability and cleanliness. In the insoluble anode copper plating system (as shown in Figure 2), the trouble of stability and cleanliness of the chemical solution can be eliminated. The main reason is that the supply of copper is outside the electroplating tank 200. The chemical solution is easy to achieve cleanliness by filtration, and the copper concentration is added by analysis, which makes it easier to obtain the stability of the chemical solution. Insoluble anode < Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ------------- Order --------- Line --- -------------------------- This paper size is applicable to National Standard (CNS) A4 (210 X 297 mm) ΐ 4 6 9 3 0 4 A7 — B7 V. Description of the invention (210 uses iridium oxide or platinum, its power line is stable, and it also helps the copper plating uniformity, as shown in Figure 3 comparing the distribution of power lines 150 and 250 of two copper plating systems. At the same time, the gloss agent only needs Considering the consumption of anode 210 oxidation, the stability of the chemical solution is higher. Traditional copper plating methods for soluble anodes have low copper source costs and do not require additional electricity for copper dissolution, so unless they are special or high-quality products In general, copper plating methods for insoluble anodes are not used. However, with the trend of thinner and lighter electronic products, insoluble anode copper plating systems will increase in the future. Further consideration of copper plating methods for insoluble anodes currently exists on the market. The supply can be divided into three types: 1. Electrolytically dissolve copper and cooperate with ion exchange membrane Copper is separated in a copper-dissolving bath. The system has many side effects, as detailed below: (1) Because copper ions cannot be filtered out 100%, a small amount of copper deposited on the cathode exists in powder form, resulting in waste generation. (2) ) The life of the ion exchange membrane is not long, and the system is prone to damage the diaphragm due to poor sealing, resulting in a significant increase in maintenance costs. (3) The gloss agent will still be consumed by electrolysis, and the cost of the chemical solution will be much higher. 2. Pass in oxygen and ozone Or ferric oxide dissolving copper such as ferric iron: The advantage of this method is that there is no problem of co-deposition of metal impurities, and the source cost of copper is also low. The main problem comes from the gloss agent. It is easy to be damaged by oxidation and cause a lot of loss of the gloss agent. At the same time, the cracked product may also cause the deterioration of copper quality. 3. Add anion-removable copper salts such as copper oxide (CuO) or copper carbonate (CuC03) as Copper supplement method. This method has a small effect on the glossing agent. ------: -------_ 1 (Please read the precautions on the back before filling this page) Magic ·-Line. Intellectual property of the Ministry of Economic Affairs Printed on paper Standards are applicable to China National Standard (CNS) A4 specifications (210 297 public love) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 693 04 A7 _____ B7 V. Description of the invention (>) and low maintenance costs, but there are still side effects, The main problems are as follows: (1) Recovered copper is often used in the production of outsourced copper salts, so it is difficult to control its metal impurities, such as Zn, Fe, Pb, Ni, etc. Such impurities will jointly precipitate and affect the structure of the copper layer, or affect after accumulation. The balance of sulfate in the plating solution. (2) The cost of purchased copper salts is high, especially those with high purity (40 ~ 90% higher than the copper source used in the soluble anode copper plating system). Also consider copper salts (such as sulfuric acid (Such as copper, copper chloride, etc.), it is very easy to form copper hydroxide precipitation in alkaline environment with pH greater than 7.9. Copper hydroxide is insoluble in water, but soluble in β in acidic environment and in alkaline environment with pH less than 13, copper solubility can also be controlled at ppm level. The copper hydroxide added to the copper plating solution will react with sulfuric acid to produce copper sulfate for electroplating. The only by-product is water. Compared with copper carbonate, there are some carbonic acid residues that need to be purged and the solubility of copper oxide is poor. Copper hydroxide has advantages as a copper supply source for insoluble anode copper plating methods. In the traditional process of making copper oxide, copper hydroxide or copper carbonate, recycled copper is often used as a raw material, but because the source of recovered copper is too complicated, there are often metal impurities such as Ni, Cr, Pb, Zn, and Fe, and such impurities It will precipitate together during electroplating and affect the copper layer structure (such as the formation of copper nodules and reduced tensile resistance). In high-end products, Pb eutectoid will cause alpha particles and affect 1C quality. In contrast, PCB factories often have a large amount of copper-containing waste liquid, which is traditionally recovered in the form of copper sulfate. Since the PCB plant has a simpler type of raw materials ‘recovered copper salts are less likely to contain other metal impurities, the copper salts made from them are very suitable for electroplating’ but the problem of anion accumulation still needs to be avoided. 5 This paper size applies to China National Standard (CNS) A4 (· 21〇 X 297 public love) I !! 1! 3 'wave! — Order! —! -Line ------------ I --- III I ----- ν'--、. '·-' (Please read the notes on the back before filling this page) 4 6 9304 V. Description of the invention (f) [Objective and description of the invention] (Please read the note on the back before filling this page) Accordingly, the object of the present invention is to provide an improved insoluble anode copper plating method, which can avoid the above-mentioned practice. Disadvantages of known technology, the possibility of replacing traditional soluble anode systems with accelerated insoluble anode systems. The present invention replaces the copper carbonate and copper oxide in the traditional process with another recovered copper hydroxide as a copper supplementary source for the insoluble anode copper plating system, and achieves the above-mentioned object. Not only can it significantly reduce the metal impurities in the traditional copper carbonate and copper oxide recycling process, reduce the problems such as copper nodules or reduced tensile strength, but also significantly reduce the raw material cost of insoluble anode copper plating, which also has the effect of resource recovery. . According to the method of the present invention, a copper plating system using an insoluble anode is provided, which has a copper-dissolving tank as a source for supplementing copper ions, which can receive copper-containing electrolyte from the copper-plating tank and supplement copper according to the concentration of copper ions therein. Back to the copper plating tank. The method is characterized in that the source of supplemented copper ions in the copper bath is recovered copper hydroxide. The process of recovery and preparation includes: adding a copper salt aqueous solution recovered by a PCB factory to an alkaline solution, and when the pH is controlled between 8 and 13. A large amount of precipitates that are insoluble in water are generated, and the obtained precipitates are washed with water to remove the remaining water-soluble salts, and copper hydroxide powder is obtained after drying. '' Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Simplified description of the diagram] Figure 1 is a city map of the soluble anode ore copper system. Figure 2 is the 7ft intention β of the insoluble anode copper plating system. Figure 3 is a comparison of the power line distribution of the soluble and insoluble anodes. 6 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 93 0 4 A7 B7 V. Description of the invention (y) [Illustration of reference symbols in drawings] 100 Copper plating tank 110 Anode titanium basket 111 Phosphor copper ball 112 Anode bag 113 Anode guide rod 120 Cathode plating 150 Power line 200 Copper plating tank 210 Insoluble anode 211 'Anode guide plate 220 Cathode plating 230 Copper concentration detector 240 Dissolved copper Tank 250 power line [Detailed description of the invention] The insoluble anode copper plating method according to the present invention includes: providing a copper plating tank 200, including an insoluble anode 210, a plated part 220 as a cathode, and a copper-containing electrolyte; providing a copper Concentration detector 230 to detect the concentration of copper ions in the copper plating tank; a copper dissolving tank 240 is provided as a source for supplementing copper ions, and it can receive the copper-containing electrolyte from the copper plating tank 200. After supplementing the copper concentration, the copper is returned to the copper plating tank 200; an effective voltage is applied between the cathode and the anode to cause the copper in the copper-containing electrolyte to precipitate out on the plating 220. This method is characterized in that the source of copper ions in the copper bath 240 is 7 The paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) — — — — — — 1 — 117- ^^ i! Order 1! 1 (please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperative 469304 A7 __B7______ V. Description of the invention (^;) The recovered copper hydroxide, the process of its recovery and preparation includes : Add the copper salt solution recovered by the PCB factory to the lye. When the pH is controlled at 8 ~ 13, a large amount of water-insoluble precipitates are generated. The obtained precipitates are washed with water to remove the remaining water-soluble salts and dry After that, copper hydroxide powder was obtained. The basic structure of the method of the present invention is similar to the conventional insoluble anode copper plating method and system, as shown in Fig. 2, for example, which are well known to those skilled in the art, so the operation method is not repeated here. The improvement and characteristics of the present invention are that the copper ions are supplemented with recovered copper hydroxide, and the process of recovery and preparation is described as follows: The copper salt recovered by the PCB factory is dissolved in water to form a copper salt aqueous solution, or for example, direct plating is used. As a copper salt aqueous solution, the copper solution is directly added to the lye solution with a precisely calculated concentration. When the pH is controlled between 8 and 13, a large amount of copper hydroxide insoluble precipitate can be formed. The obtained copper hydroxide precipitate can be washed with water to remove the remaining water-soluble salts, and it can be used after drying. The alkaline solution used is preferably an aqueous solution of lithium, sodium, and potassium hydroxides, because the copper salts recovered by general PCB factories are mostly sulfates, chlorides, or nitrates, and lithium, sodium, and potassium are compounded with it. The generated salts are very easily soluble in water, so the generated salts can be removed with a larger amount of water. The speed and agitation of the copper salt solution will affect the copper oxide eutectoid ratio, and the drying temperature will also affect the copper oxide formation ratio. The ratio of copper oxide to argon copper oxide will affect the dissolution rate, so this ratio should be reduced as much as possible. For example, the copper salt solution should not be added too quickly, and it is best to continue stirring the lye. The baking temperature of the copper hydroxide precipitate is, for example, preferably between 70 ° C and 110 ° C to reduce the probability of copper oxide formation. 8 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I II I I --- 1 name! Order! !! Line /! ... I (Please read the precautions on the back before seeing this page) 4693 04 A7 B7 V. Description of the invention (γ) The pH of the filtrate after the precipitation of copper hydroxide should be controlled in the range of 8 ~ 13 In order to avoid the accumulation of excessive copper ions in the filtered waste liquid and water washing liquid, it is also beneficial to environmental protection. Another preparation method can use the alkaline solution of carbonate of lithium, sodium and potassium to replace the alkaline solution of hydroxide, and the resulting precipitate is copper carbonate (containing crystal water), and then baked at a higher temperature, such as 200 ~ 25 (TC In the meantime, the carbon dioxide can be driven out to form copper hydroxide, and the residual carbonic acid can be reduced. If an aqueous carbonate solution of lithium, sodium, and potassium is used, only the excessive addition can control the amount of copper ions in the subsequent washing solution- The basic function of the copper-dissolving tank 240 in the present invention is the same as that of a known person, that is, as a source for supplementing copper ions, it can receive the copper-containing electrolyte from the copper-plating tank 200 and cooperate with the automatic sampling analysis of the copper concentration detector 230 The copper hydroxide added is then added, and the copper-containing electrolyte is returned to the copper plating tank 200. Of course, the copper-containing electrolyte can be filtered during the flow through the copper-dissolving tank 240 to maintain the cleanliness of the chemical solution. The insoluble anode copper plating system can also be matched with a plating buffer system (not shown in Figure 2), which will help the stability of the copper plating system. The following demonstrates the recovery and preparation of three types of copper hydroxide: Section 1 50 liters of copper plating solution , Its ingredients are: copper sulfate 75 g / l, sulfuric acid .200 g / l, chlorine content 35 ppm, and several brighteners. Alkaline 50 l, its composition is: sodium hydroxide 200 g / l Preparation method: Continuously stirring the lye, And add copper plating 9 in a volume ratio of 1: 1 — — — — — — — II II (Please read the precautions on the back before filling in this page)
V 線. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格<210 x 297公楚） 4 6 93 04 A7 B7 五、發明說明（y) 液。添加速度約爲每分鐘5升，此時即會生成氫氧化銅深 藍黑色沉澱。鍍銅液加完後再加入200升去離子水，此時 pH値約爲12〜13，攪拌使沉降物懸浮，之後抽入過濾機 以#1000篩濾出氫氧化銅。.此時濾液中銅濃度約爲 6~8ppm。所得濾餅以200升去離子水淸洗後，送入烘箱 以85°C、60分鐘烘烤去水，所得氫氧化銅約1.4公斤， 純度大於98%。 範例2 回收銅鹽水溶液50升，其成分爲：硫酸銅250克/升。 鹼液50升，其成分爲：氫氧化鉀120克/升。 製備方式：持續攪拌鹼液，並以1:1之體積比例添加回收 銅鹽水溶液。添加速度約爲每分鐘10升，此時即會生成 氫氧化銅淡藍色沉澱。回收銅鹽水溶液加完後再加入300 升去離子水，此時pH値約爲12，攪拌使沉降物懸浮，之 後抽入過濾機以#1000篩濾出氫氧化銅，濾液此時銅濃度 約爲6~8ppm。所得濾餅再以400升去離子水淸洗後，送 入烘箱以85°C、60分鐘烘烤去水，所得氫氧化銅約4.5 公斤，純度大於98%。 範例3 回收銅鹽水溶液50升，其成分爲：硫酸銅250克/升。 鹼液50升，其成分爲：碳酸鈉大於11〇克/升。 製備方式：持續攪拌鹼液，並以1:1之體積比例添加回收 銅鹽水溶液。添加速度約爲每分鐘5升，此時即會生成碳 10 本纸張尺度適用t國國家標準（CNS)A4規格（210 X 297公笼） — III * I , { J (請先閱讀背面之注意事項再^寫本頁) iJ· -線· 經濟部智慧財產局員工消費合作社印製 A7 4 6 9 3 0 4: B7 五、發明說明（y^ 酸銅淡藍綠色結晶沉澱以及大量氣泡產生。回收銅鹽水溶 液加完後再加入300升去離子水，攪拌使沉降物懸浮’之 後抽入過濾機以#1000篩濾出碳酸銅結晶，濾液此時銅濃 度約爲5PPm。所得濾餅再以4〇〇升去離子水淸洗後’送 入烘箱以200°C、60分鐘烘烤去水排氣，所得氫氧化銅約 4.8公斤（因顆粒較大，回收率高），純度大於98%。 雖然本發明已揭示如上，然而熟於此技藝者將可體認 到：在不偏離本發明的精義和範疇下，可在形式上和細節 上做改變。所述的範例於各方面應考慮爲示範性的，而非 限制性的。因此，本發明的範圍應由所附的申請專利範圍 所限定，而非單由前面的敘述來界定。凡本發明的等效者 和相關的改變，均應包含於申請專利範圍之中。 -------------裝— (請先閱讀背面之注意事項再¢(寫本頁) 訂. -線- 經濟部智慧財產局員工消費合作社印製 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚）Line V. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 Specification < 210 x 297 Gongchu. 4 6 93 04 A7 B7 V. Description of Invention (y). The addition rate is about 5 liters per minute, at which time a dark blue-black precipitate of copper hydroxide is formed. After the addition of the copper plating solution, 200 liters of deionized water was added. At this time, the pH was about 12-13, and the precipitate was suspended by stirring. Then, the copper hydroxide was filtered out by a # 1000 sieve. At this time, the copper concentration in the filtrate is about 6 ~ 8ppm. The obtained filter cake was washed with 200 liters of deionized water, and then sent to an oven to bake water at 85 ° C for 60 minutes. The obtained copper hydroxide was about 1.4 kg and the purity was greater than 98%. Example 2 50 liters of copper salt solution was recovered, and its composition was 250 g / L of copper sulfate. 50 liters of lye, its composition is: 120 g / L of potassium hydroxide. Preparation method: keep stirring the lye, and add and recover the copper salt aqueous solution in a volume ratio of 1: 1. The addition rate is approximately 10 liters per minute, at which time a pale blue precipitate of copper hydroxide is formed. After the recovery of the copper salt solution, add 300 liters of deionized water. At this time, the pH value is about 12, and the precipitate is suspended by stirring. After that, the copper hydroxide is filtered through a # 1000 sieve to filter out the copper concentration. It is 6 to 8 ppm. The obtained filter cake was washed with 400 liters of deionized water, and then sent to an oven to bake water at 85 ° C for 60 minutes. The obtained copper hydroxide was about 4.5 kg and the purity was greater than 98%. Example 3 50 liters of copper salt solution was recovered, and its composition was 250 g / L of copper sulfate. 50 liters of lye, its composition is: sodium carbonate is more than 110 g / L. Preparation method: keep stirring the lye, and add and recover the copper salt aqueous solution in a volume ratio of 1: 1. The adding speed is about 5 liters per minute, and carbon 10 will be generated at this time. The paper size is applicable to the national standard (CNS) A4 specification (210 X 297 male cage) — III * I, {J (Please read the Note ^ Write this page again) iJ · -line · Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 4 6 9 3 0 4: B7 V. Description of the invention (y ^ light blue-green crystal precipitation of copper acid and a large number of bubbles generated After the recovery of the copper salt solution was added, 300 liters of deionized water was added, and the sediment was suspended to stir the precipitate. Then, it was drawn into a filter to filter out the copper carbonate crystals with a # 1000 sieve, and the copper concentration of the filtrate at this time was about 5 PPm. After washing with 400 liters of deionized water, it was sent to an oven and baked at 200 ° C for 60 minutes to remove water and exhaust. The obtained copper hydroxide was about 4.8 kg (due to the larger particles, the recovery rate was higher), and the purity was greater than 98. Although the present invention has been disclosed as above, those skilled in the art will recognize that changes can be made in form and details without departing from the spirit and scope of the present invention. The examples described should be used in various aspects. It is considered exemplary rather than limiting. Therefore, the present invention The scope should be defined by the scope of the attached patent application, not just the foregoing description. All equivalents and related changes of the present invention should be included in the scope of patent application. ------ ------- Installation— (Please read the precautions on the back before you write this page). -Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 11 This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 cm)