200412330 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種用於電子工業製程中，例如導線架 或印刷電路板之酸性含銅廢液的資源化處理方法。更定而 言之’本發明係關於一種去除酸性含銅廢液（包括硫酸銅 廢液、氯化銅廢液、硝酸銅廢液等）中銅離子之方法，並 將去除銅離子後的液體轉化成廢水凝集劑或硫酸亞鐵、氯 化亞鐵、硝酸亞鐵等亞鐵鹽類或硫酸鐵、氯化鐵、硝酸鐵 等鐵鹽類。 【先前技術】 隨著電子資訊工業的進步，相關印刷電路板工業亦不 斷的擴充，而印刷電路板的製造過程中，常常會有酸性含 銅廢液，包括電鍍廢液、微蝕廢液及蝕刻廢液等的大量產 生，因而造成環保上嚴重的問題。 上述廢液主要成份爲Cu2+(含量爲10〜150g/L)、 Cl·或S04_2(含量爲150〜200g/L);若未能有效的處理 這些含銅廢液，勢必對環境產生重大的影響，導致嚴重的 危害；因此，有必要妥善處理此類酸性含銅廢液以避免造 成環境污染。 目前習用的處理方法是以管末處理方式，利用添加氫 氧化鈉中和酸性含銅廢液中的游離酸，調整pH値至8〜13 使大部份銅離子形成氫氧化銅污泥沉澱析出，此種處理方 法雖可有效降低銅離子濃度，但對於游離酸根離子，包括 硫酸根離子、氯離子、硝酸根離子並不能得到良好的效果 200412330 ，且同時產生大量的污泥亦會對環境發生嚴重的影響，增 加後處理的成本。 另一習用處理流程爲將上述氫氧化銅污泥加入硫酸溶 液中形成硫酸銅結晶，此種作法可得到純度相當高的硫酸 銅結晶，但仍然存在游離酸根離子無法處理及飽和硫酸銅 液體二次污染問題。 中華民國專利公告號212787，標題爲「處理酸性氯化 銅廢液以回收銅及衍生多元氯化鋁之製程」中，其利用鋁 金屬置換氯化銅廢液中的銅離子，產生銅及衍生多元氯化 鋁，該製程理論上雖可達到廢液完全資源化的目的，但在 實際生產過程時，隨著酸的消耗，反應速度會迅速減緩， 造成處理時間長及反應不良的現象，其生成的多元氯化鋁 存在銅含量偏高的問題（殘留銅含量約爲0.3〜5.Og/L) ，導致再生利用的不安定性；此外，反應生成的銅粉常有 氧化亞銅及氧化銅混雜其中。 另外，中華民國專利公告號249221係關於「酸鹼性蝕 銅廢液之回收處理方式」，其說明利用加熱曝氣方式去氨 後，以調整pH、加熱方式產生氧化銅，此種作法主要用於 氨水系列的含銅廢液，並不適合用於酸性含銅廢液；此外 ，此種作法產生的氧化銅存有廢液体積不斷增加、大量消 耗能源、液鹼用量大、銨離子及氯離子污染無法去除及二 次污染等問題，基本上爲不具經濟性的處理方法。 再者，中華民國專利公告號367308係關於「氯化銅溶 液轉換成銅金屬氧化物之方法」，其揭示利用二次置換方 200412330 式，以鋁金屬置換氯化銅廢液中的銅離子，產生銅及衍生 多元氯化鋁，該製程確可達到廢液完全資源化的目的，其 生成的多元氯化鋁純度也高（殘留銅含量約爲0.1〜0.3g/ L)。唯一缺點爲只適用於氯化銅溶液（因爲在硫酸溶液中 ，鋁會鈍化造成反應停頓）。另外，此專利生成的多元氯 化錦（P〇ly_Aluminum Chloride，PAC)由於凝聚性佳，爲 廢水處理系統常用的凝集劑，但由於其形成的膠羽比重輕 ，不易沉降，故一般多以搭配硫酸亞鐵或氯化鐵來操作。 【發明內容】 本發明之目的爲提供一種利用金屬鐵置換法去除酸性 含銅廢液（包括硫酸銅廢液、氯化銅廢液、硝酸銅廢液等 )中銅離子之方法，其包括： ⑴一次置換：將鐵金屬（包括鐵粉、鐵片及鐵塊）置 入酸性含銅廢液中進行置換反應，沈澱出銅金屬固體，予 以過濾； (ii) 二次置換：將鐵金屬置入上述已去除銅的酸性液中 進行反應，使殘留的酸和鐵作用，提高廢液中鐵含量，及 進行過濾；及 (iii) 純化：將沈澱出銅金屬固體，置入未處理的酸性含 銅廢液新液中，利用其所含酸洗去殘留在銅中的鐵。 特別是，本發明係關於一種利用金屬鐵置換法去除酸 性含銅廢液（包括硫酸銅廢液、氯化銅廢液、硝酸銅廢液 等）中銅離子之方法，其包括： ⑴一次置換：將鐵金屬（包括鐵粉、鐵片及鐵塊）置 200412330 入酸性含銅廢液中進行置換反應，沈澱出銅金屬固體，予 以過濾； (ii) 二次置換：將鐵金屬置入上述已去除銅的酸性液中 進行反應，使殘留的酸和鐵作用，提高廢液中鐵含量，及 進行過濾； (iii) 純化：將沈澱出銅金屬固體，置入未處理的酸性含 銅廢液新液中，利用其所含酸洗去殘留在銅中的鐵； (IV) 安定化：將純化完成的銅金屬固體，作適度的銅面 處理，使銅金屬固體乾燥而不易氧化；及 (V) 磁選：利用電磁鐵設計，確保銅金屬固體中的鐵完 全去除。 本發明之一具體實例爲在步驟（ii)所得之濾液經調整後 可作爲廢水處理所需之凝集劑。 本發明之另一具體實例爲在步驟（V)所得之銅金屬純度 達99.5%以上。 本發明之另一具體實例爲在步驟（v)所得之銅金屬經氧 化處理可得氧化銅粉末，純度達99.5%以上。 發明詳述 本發明的技術主要是保留中華民國專利公告號367308 之精神，以鐵代替鋁進行置換，可處理的廢液也由原來的 氯化銅廢液擴充成酸性含銅廢液，包括硫酸銅廢液、硝酸 銅廢液、氯化銅廢液等，配合流程設計的改善，達到快速 而有效的處理目的。根據本發明之方法包括：一次置換爲 高濃度銅的置換，其作法爲在一次置換中加入適量鐵金屬 200412330 於酸性含銅廢液中行置換反應，沈澱出銅金屬固體，予以 過濾；二次置換則將足量鐵金屬置入上述已去除銅的酸性 液中二次反應，其目的爲將低濃度的銅完全去除然後，並 使殘留的酸和鐵作用，提高廢液中鐵含量，以合乎成品規 格；同時將沈澱出銅金屬固體，以未處理的酸性含銅廢液 新廢液洗去殘留在銅中的鐵，達到純化的目的；純化過的 銅金屬固體，經適度的銅面處理及電磁鐵的磁選步驟，即 可得到純度極高的銅金屬固體。二次置換反應所得之濾液 (FeS04)經調整後可作爲廢水處理所需之凝集劑。 基本上而言，金屬鐵置入酸性含銅廢液中本就會進行 置換反應，但在置換過程，置換生成的銅金屬會和尙未反 應的鐵金屬產生混雜、包覆的現象，導致反應停頓及生成 物純度不良。在本發明之方法中，第一項的重點爲將含銅 酸性廢液加熱至適當溫度範圍（溫度設定爲10°C〜80°C ) 後，加入適量鐵金屬於酸性含銅廢液中行置換反應，鐵的 添加量爲含銅酸性廢液中總銅量的0.5〜4.0倍，其中酸性 含銅廢液中銅濃度約爲10〜180克/升，酸濃度約爲0.2〜 5.0N。反應過程保持攪拌均勻，其攪拌速度依處理量規模 而定，較佳攪拌速率2〜1200rpm，反應時間5〜60分鐘， 直至反應結束，即完成一次置換的步驟，之後過濾脫水。 其操作如附圖所示之酸性含銅廢液處理流程方塊圖之（B) 〇 本發明之方法第二項的重點爲二次置換，其作法類似 一次置換，但加入的鐵金屬量需比置換全部殘留的銅及酸 11 200412330 的總當量爲高，操作條件同一次置換，但反應間改爲ίο〜 120分鐘，直至ρ Η値爲約0.1 — 5.0間爲止，之後再將固 體過濾出，濾液（FeS04)經調整後可作爲水處理用之化學混 凝劑。過濾收集的固體再送入第一置換槽中和下一批的廢 液一起反應。其操作如附圖所示之酸性含銅廢液處理流程 方塊圖之（C )。 本發明之方法第三項的重點爲將一次置換所得的銅粉 送入純化槽中，以未處理的酸性含銅廢液新液打入攪拌均 勻，洗去殘留在銅中的鐵，達到純化的目的。 反應過程保持攪拌均勻，其攪拌速度依處理量規模而 定，較佳攪拌速率2〜1200rpm，反應溫度控制在20〜80°C ，反應時間爲5〜30分鐘，之後過瀘脫水。其操作如附圖 所示之酸性含銅廢液處理流程方塊圖之（A)。 本發明之方法第四項的重點爲將純化所得的銅粉送入 安定化槽，槽內先配好銅面安定劑，其主成份包括銅面抗 氧化劑及界面活性劑等；其中銅面抗氧化劑可使用的藥劑 包括（含單品或其倂用）：（一）磷酸或聚磷酸及其衍生物、 (二）二甲基銨、三甲基銨、二乙基銨、三乙基銨及其衍 生的有機錢類、（三）苯並二π坐（Benzodiazolej)、苯並三口坐 (Benzotriazole)、甲苯三唑（Tolyltriazole)等偶氮化合物、（ 四）磺酸或磺酸鹽及其衍生物等；其含量爲0.1〜5.0% ; 固體對水溶液比例爲1:1〜1:50，攪拌速率以2〜600rpm， 反應溫度控制在10〜50°C，反應時間爲5〜30分鐘，之後 過濾脫水。其操作如附圖所示之酸性含銅廢液處理流程方 12 200412330 塊圖之（D )。 本發明之方法第五項的重點爲，將安定化所得的銅粉 經過附有電磁鐵的磁選輸送機，利用磁選作用，將可能殘 留的鐵粉或鐵屑吸附以確保銅金屬固體中的鐵完全去除。 吸附的鐵粉或鐵屑則在電磁鐵磁性消失後，經震動回收。 產生的銅粉除了可直接銷售外，亦可經由乾燥烘烤轉 化成氧化亞銅或氧化銅。其中若產物希望爲氧化亞銅，則 在可在100〜150°C下真空乾燥即可；若希望產物爲氧化銅 ，則將銅粉進一步焙燒即可，溫度爲約150- 300°C，焙燒 時間爲約1至3小時。 本發明方法所具有的優點爲： ㈠經濟方面：同時具有處理酸性含銅廢液及生產高單 價工業原料（銅粉、氧化亞銅或氧化銅）及廢水處理使用 的混凝劑等多項功能； ㈡環保方面：完全回收利用，無廢水、廢氣及廢棄物 產生，因此無二次污染的顧慮； ㈢生產流程：簡易不複雜，易於控制； ㈣設備方面：設備需求簡單，合理可行； ㈥產物純度高：一次置換由於放入鐵量少於當量値， 故所得之銅純度極高，沒有鐵的殘留；而在二次置換時以 過量的鐵確保銅離子完全被置換析出，以確保溶液中銅離 子在控制濃度之下。 然而，必須了解的是雖然在前述說明中已詳細說明了 本發明的特徵和優點，但其只是說明而已，任何在本發明 13 200412330 原理下所作的修正或改良皆包括於本發明的範圍之內。 【實施方式】 運用本發明技術可輕易將酸性含銅廢液中絕大部份的 銅離子除去，使得處理後液體中所含銅離子的濃度分別低 於3Oppm，而適於調整配製成廢水凝集劑或濃縮結晶高成單 價工業原料。爲使更淸楚本發明技術的優點，茲以實施例 說明如下： 實施例1 : 取500mL電鍍銅廢液，以本發明之方法，以去除廢液 中酸及銅離子。一次置換時，於50°C加入鐵金屬20克， 反應時間30分鐘，使廢液中銅離子置換還原成銅。二次置 換時，於50°C加入鐵金屬45克，反應時時間60分鐘，使 廢液中殘留銅離子置換還原成銅，並將硫酸轉換成硫酸亞 鐵。處理前後液体中所含銅離子、鐵離子及硫酸量如表（一) 所示。由表（一）中可淸楚看出，處理後液體中銅離子含量僅 6ppm，而鐵離子含量高達128g / L，因此適用於配製成廢水 凝集劑。 項目 處理前 一次置換後 二次置換後 硫酸（N) 4.1 3.6 0.1 銅（g/L) 18.4 1.2 5.7ppm 鐵（g/L) 0 19.6 128.3 表（一） 實施例2 :200412330 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a resource treatment method for acid copper-containing waste liquid used in the process of the electronics industry, such as a lead frame or a printed circuit board. More specifically, the present invention relates to a method for removing copper ions from acidic copper-containing waste liquid (including copper sulfate waste liquid, copper chloride waste liquid, copper nitrate waste liquid, etc.), and the liquid after removing copper ions Transformed into wastewater coagulant or ferrous salts such as ferrous sulfate, ferrous chloride, and ferrous nitrate, or iron salts such as ferric sulfate, ferric chloride, and ferric nitrate. [Previous technology] With the advancement of the electronic information industry, the related printed circuit board industry has continued to expand. During the manufacturing process of printed circuit boards, there are often acidic copper-containing waste liquids, including electroplating waste liquids, micro-etching waste liquids, A large amount of etching waste liquid and the like are generated, thereby causing serious environmental problems. The main components of the above waste liquid are Cu2 + (content is 10 ~ 150g / L), Cl · or S04_2 (content is 150 ~ 200g / L); if these copper-containing waste liquids are not effectively treated, it will inevitably have a significant impact on the environment , Resulting in serious harm; therefore, it is necessary to properly dispose of such acidic copper-containing waste liquid to avoid causing environmental pollution. At present, the conventional treatment method is to treat the end of the tube by adding sodium hydroxide to neutralize the free acid in the acidic copper-containing waste liquid, and adjust the pH to 8 ~ 13 to make most of the copper ions form copper hydroxide sludge and precipitate. Although this treatment method can effectively reduce the concentration of copper ions, it does not achieve good results for free acid ions, including sulfate ions, chloride ions, and nitrate ions. 200412330, and at the same time, a large amount of sludge will also occur to the environment Serious impact, increasing the cost of post-processing. Another conventional treatment process is to add the above-mentioned copper hydroxide sludge to a sulfuric acid solution to form copper sulfate crystals. This method can obtain copper sulfate crystals of relatively high purity, but there are still free acid ions that cannot be treated and saturated copper sulfate liquid can be used twice. pollution problem. Republic of China Patent Bulletin No. 212787, titled "Process for Processing Acid Copper Chloride Waste Liquid to Recover Copper and Derive Multiple Aluminum Chloride", which uses aluminum metal to replace copper ions in copper chloride waste liquid to produce copper and derivatives Polyaluminium chloride, although this process can theoretically achieve the purpose of completely recycling waste liquid, in the actual production process, with the consumption of acid, the reaction speed will quickly slow down, resulting in long processing time and poor reaction. The generated polyaluminum chloride has a problem of high copper content (residual copper content is about 0.3 ~ 5.Og / L), which leads to the instability of recycling. In addition, the copper powder produced by the reaction often has cuprous oxide and copper oxide. Miscellaneous. In addition, the Republic of China Patent Bulletin No. 249221 is about "recycling and treating methods of acidic and alkaline copper etching waste liquid", which explains that after removing ammonia by heating and aeration, copper oxide is produced by adjusting the pH and heating. This method is mainly used The copper-containing waste liquid in the ammonia water series is not suitable for acidic copper-containing waste liquid. In addition, the copper oxide produced by this method has an increasing volume of waste liquid, a large amount of energy consumption, a large amount of liquid alkali, ammonium ions and chloride ions. Problems such as the inability to remove pollution and secondary pollution are basically non-economical treatment methods. Furthermore, the Republic of China Patent Bulletin No. 367308 is about "Method for Converting Copper Chloride Solution to Copper Metal Oxide", which discloses the use of the secondary substitution formula 200412330 to replace copper ions in copper chloride waste liquid with aluminum metal. Copper and derived polyaluminum chloride are produced. This process can indeed achieve the purpose of completely recycling the waste liquid. The polyaluminium chloride produced is also high in purity (residual copper content is about 0.1 ~ 0.3g / L). The only disadvantage is that it is only suitable for copper chloride solution (because in the sulfuric acid solution, aluminum will passivate and stop the reaction). In addition, Poly-Aluminum Chloride (PAC) produced by this patent is generally used as a coagulant in wastewater treatment systems due to its good cohesiveness. However, it is generally used in combination because it forms a light plume and is not easy to settle. Ferrous sulfate or ferric chloride. [Summary of the Invention] The purpose of the present invention is to provide a method for removing copper ions in acidic copper-containing waste liquid (including copper sulfate waste liquid, copper chloride waste liquid, copper nitrate waste liquid, etc.) using a metal iron replacement method, including: ⑴One replacement: Place ferrous metal (including iron powder, iron flakes, and iron blocks) in an acidic copper-containing waste liquid for replacement reaction, precipitate copper metal solids, and filter; (ii) Second replacement: place ferrous metal Into the above copper-removed acidic solution to carry out the reaction, so that the residual acid and iron interact, increase the iron content in the waste liquid, and perform filtration; and (iii) purification: the copper metal solid precipitated out and placed in the untreated acidic In the new copper-containing waste liquid, the iron remaining in the copper is removed by using the acid contained therein. In particular, the present invention relates to a method for removing copper ions in acidic copper-containing waste liquid (including copper sulfate waste liquid, copper chloride waste liquid, copper nitrate waste liquid, etc.) by using a metal iron replacement method, including: : Place ferrous metal (including iron powder, iron flakes and iron blocks) in 200412330 into acidic copper-containing waste liquid for substitution reaction, precipitate copper metal solids, and filter; (ii) Secondary replacement: put ferrous metal into the above The copper-removed acidic liquid is reacted to react with the residual acid and iron to increase the iron content in the waste liquid and filtered; (iii) purification: the copper metal solid is precipitated and placed in the untreated acidic copper-containing waste In the new liquid, use the acid contained in it to wash away the iron remaining in the copper; (IV) Stabilization: the purified copper metal solids are treated with a moderate copper surface to dry the copper metal solids and prevent oxidation; and (V) Magnetic separation: the use of an electromagnet design to ensure the complete removal of iron from copper metal solids. A specific example of the present invention is that the filtrate obtained in step (ii) can be used as a coagulant for wastewater treatment after being adjusted. Another specific example of the present invention is that the copper metal obtained in step (V) has a purity of more than 99.5%. Another specific example of the present invention is that the copper metal obtained in step (v) can be subjected to oxidation treatment to obtain copper oxide powder with a purity of more than 99.5%. Detailed description of the invention The technology of the present invention is mainly to retain the spirit of the Republic of China Patent Publication No. 367308, and replace iron with iron instead of aluminum. The treatable waste liquid is also expanded from the original copper chloride waste liquid to an acidic copper-containing waste liquid, including sulfuric acid. Copper waste liquid, copper nitrate waste liquid, copper chloride waste liquid, etc., with the improvement of process design, achieve the purpose of fast and effective treatment. The method according to the present invention includes: one-time replacement with high-concentration copper replacement. The method is to add an appropriate amount of iron metal 200412330 to one-time replacement in an acidic copper-containing waste liquid to precipitate a copper metal solid and filter; Then, a sufficient amount of iron metal is placed in the above-mentioned copper-removed acidic liquid for a secondary reaction, the purpose of which is to completely remove low-concentration copper, and then make the residual acid and iron interact to increase the iron content in the waste liquid to meet the requirements. Finished product specifications; At the same time, copper metal solids are precipitated, and the iron remaining in copper is washed away with new untreated acidic copper-containing waste liquid to achieve the purpose of purification; the purified copper metal solids are treated with a moderate copper surface And the magnetic separation step of the electromagnet, a copper metal solid with extremely high purity can be obtained. The filtrate (FeS04) obtained from the secondary displacement reaction can be adjusted to be used as a coagulant for wastewater treatment. Basically, metal iron will undergo a substitution reaction when it is placed in an acidic copper-containing waste liquid. However, during the replacement process, the copper metal generated by the substitution will be mixed and coated with the unreacted iron metal, resulting in a reaction. Pauses and poor product purity. In the method of the present invention, the main point of the first item is to heat the copper-containing acidic waste liquid to an appropriate temperature range (the temperature is set to 10 ° C ~ 80 ° C), and then add an appropriate amount of iron metal to the acidic copper-containing waste liquid for replacement. In the reaction, the amount of iron added is 0.5 to 4.0 times the total copper amount in the copper-containing acidic waste liquid, wherein the copper concentration in the acidic copper-containing waste liquid is about 10 to 180 g / liter, and the acid concentration is about 0.2 to 5.0 N. The reaction process is kept stirring uniformly, and the stirring speed depends on the processing capacity scale. The preferred stirring rate is 2 to 1200 rpm, and the reaction time is 5 to 60 minutes. Until the reaction is completed, the replacement step is completed, and then the filter is dehydrated. The operation is as shown in the block diagram of the acidic copper-containing waste liquid treatment process (B). The second point of the method of the present invention is the second replacement. The method is similar to the one replacement, but the amount of iron metal added needs to be greater than The total equivalent of replacing all remaining copper and acid 11 200412330 is high, the operating conditions are the same replacement, but the reaction interval is changed to ο ~ 120 minutes, until ρ Η 値 is about 0.1-5.0, and then the solid is filtered out, The filtrate (FeS04) can be used as a chemical coagulant for water treatment after adjustment. The solid collected by filtration was sent to the first displacement tank and reacted with the next batch of waste liquid. Its operation is shown in the block diagram (C) of the acidic copper-containing waste liquid treatment process shown in the drawing. The third point of the method of the present invention is to send the copper powder obtained by one replacement into a purification tank, and use a new untreated acid copper-containing waste liquid to stir into it, wash away the iron remaining in the copper, and achieve purification. the goal of. The reaction process is kept stirring uniformly, and the stirring speed depends on the processing capacity scale. The preferred stirring rate is 2 to 1200 rpm, the reaction temperature is controlled to 20 to 80 ° C, the reaction time is 5 to 30 minutes, and then dehydration is carried out. Its operation is shown in the block diagram (A) of the acidic copper-containing waste liquid treatment process shown in the drawing. The focus of the fourth item of the method of the present invention is to send the purified copper powder to a stabilization tank. The copper surface stabilizer is firstly prepared in the tank. Its main components include copper surface antioxidants and surfactants. Among them, copper surface resistance Agents that can be used as oxidants include (including single products or their use): (a) phosphoric acid or polyphosphoric acid and its derivatives, (b) dimethylammonium, trimethylammonium, diethylammonium, and triethylammonium And its derived organic money, azo compounds such as (3) Benzodiazolej, Benzotriazole, Tolyltriazole, (4) sulfonic acid or sulfonate, and Derivatives, etc .; its content is 0.1 ~ 5.0%; the ratio of solid to aqueous solution is 1: 1 ~ 1: 50, the stirring rate is 2 ~ 600rpm, the reaction temperature is controlled at 10 ~ 50 ° C, and the reaction time is 5 ~ 30 minutes, It is then filtered and dehydrated. The operation is shown in the drawing (D) of the block diagram of the acidic copper-containing waste liquid treatment process shown in the drawing. The fifth point of the method of the present invention is to pass the copper powder obtained by stabilization through a magnetic separation conveyor with an electromagnet, and use magnetic separation to adsorb possible residual iron powder or iron filings to ensure iron in copper metal solids. Remove completely. The adsorbed iron powder or iron filings are recovered by vibration after the magnetism disappears. The produced copper powder can not only be sold directly, but also be converted into cuprous oxide or copper oxide through dry baking. Among them, if the product is intended to be cuprous oxide, it can be dried under vacuum at 100 ~ 150 ° C; if the product is intended to be cupric oxide, the copper powder can be further roasted, and the temperature is about 150-300 ° C. The time is about 1 to 3 hours. The method of the invention has the following advantages: (1) Economic aspects: it has multiple functions such as processing acidic copper-containing waste liquid and producing high unit price industrial raw materials (copper powder, cuprous oxide or copper oxide) and coagulant for wastewater treatment; ㈡Environmental protection: complete recycling, no waste water, waste gas and waste, so no concerns about secondary pollution; ㈢ production process: simple and uncomplicated, easy to control; ㈣ equipment: simple equipment requirements, reasonable and feasible; ㈥ product purity High: Because the amount of iron is less than the equivalent 値 in a single replacement, the copper obtained is extremely pure and there is no iron residue; and in the second replacement, the excess iron is used to ensure that the copper ions are completely replaced and precipitated to ensure the copper in the solution. Ions are under controlled concentration. However, it must be understood that although the features and advantages of the present invention have been described in detail in the foregoing description, it is only an illustration, and any amendment or improvement made under the principle of the invention 13 200412330 is included in the scope of the invention . [Embodiment] By using the technology of the present invention, most of the copper ions in the acidic copper-containing waste liquid can be easily removed, so that the concentration of copper ions in the treated liquid is lower than 30 ppm, respectively, which is suitable for adjusting the preparation of wastewater. Agglutinating agent or concentrated crystals are high-priced industrial raw materials. In order to better understand the advantages of the technology of the present invention, the following examples are used to illustrate the following: Example 1: 500 mL of copper electroplating waste liquid is taken and the method of the present invention is used to remove acid and copper ions in the waste liquid. For one replacement, 20 g of iron metal was added at 50 ° C, and the reaction time was 30 minutes, so that copper ions in the waste liquid were replaced and reduced to copper. During the second replacement, 45 g of iron metal was added at 50 ° C, and the reaction time was 60 minutes. The residual copper ions in the waste liquid were replaced and reduced to copper, and sulfuric acid was converted to ferrous sulfate. The amount of copper ions, iron ions and sulfuric acid in the liquid before and after the treatment are shown in Table (1). It can be clearly seen from Table (1) that the content of copper ions in the treated liquid is only 6 ppm, while the content of iron ions is as high as 128 g / L, so it is suitable for the formulation of wastewater agglutinants. Item Before treatment After the first replacement After the second replacement Sulfuric acid (N) 4.1 3.6 0.1 Copper (g / L) 18.4 1.2 5.7ppm Iron (g / L) 0 19.6 128.3 Table (I) Example 2:
取500ml氯化銅蝕刻廢液，依照實施例1所述步驟對 廢液進行置換。操作條件局部修改爲一次置換時，於40°C 14 200412330 加入鐵金屬80克，反應時間20分鐘，使廢液中銅離子置 換還原成銅。二次置換時，於50°C加入鐵金屬30克，反 應時時間60分鐘，使廢液中殘留銅離子置換還原成銅，並 將鹽酸轉換成氯化亞鐵。處理前後液體中所含銅離子、鐵 離子及硫酸量如表（二）所示。由表（二）中可淸楚看出，處理 後液體中銅離子含量僅13ppm，而鐵離子含量高達220g / L ’其濃度已超出規格上限，經調整適用於配製成廢水凝集 劑0 項目 處理前 一次置換後 二次置換後 鹽酸（N) 2.6 2.1 0.01 銅（g/L) 162 7.8 12ppm 鐵（g/L) 0 160 220 表（二） 實施例3 : 取500mL微蝕廢液，依照實施例1所述之條件和步驟 對廢液進行置換，處理前後液体中所含銅離子、鐵離子及 硫酸量如表（三）所示。由表（三）中可淸楚看出，處理後液體 _ 中銅像離子含量僅4ppm，而鐵離子含量高達84g / L，因此 適用於配製成廢水凝集劑。 項目 處理前 一次置換後 二次置換後 硫酸（N) 2.2 1.8 0.1 銅（g/L ) 25 0.8 3.4ppm 鐵（g/L) 0 25 84 表（三） 15 200412330 【圖式簡單說明】 (一） 圖式部分 第一圖係爲本發明方法的流程圖。 (二） 元件代表符號 A 純化 B 一次置換 C 二次置換 D 安定化 E 磁選 16500 ml of copper chloride etching waste liquid was taken, and the waste liquid was replaced according to the procedure described in Example 1. When the operating conditions were partially changed to a single replacement, 80 g of iron metal was added at 40 ° C 14 200412330, and the reaction time was 20 minutes. The copper ions in the waste liquid were exchanged and reduced to copper. During the second replacement, 30 g of iron metal was added at 50 ° C, and the reaction time was 60 minutes. The residual copper ions in the waste liquid were replaced and reduced to copper, and hydrochloric acid was converted to ferrous chloride. The amount of copper ions, iron ions and sulfuric acid in the liquid before and after the treatment are shown in Table (2). It can be clearly seen from Table (2) that the content of copper ions in the treated liquid is only 13 ppm, while the content of iron ions is as high as 220 g / L. Its concentration has exceeded the upper limit of the specification, and it is adjusted to be used as a wastewater agglutinant. Hydrochloric acid (N) after the first replacement after the treatment 2.6 2.1 0.01 Copper (g / L) 162 7.8 12ppm Iron (g / L) 0 160 220 Table (2) Example 3: Take 500mL of micro-etching waste liquid, according to The conditions and steps described in Example 1 were used to replace the waste liquid, and the amounts of copper ions, iron ions, and sulfuric acid contained in the liquid before and after the treatment are shown in Table (3). It can be clearly seen from Table (3) that the copper ion content in the treated liquid _ is only 4 ppm, and the iron ion content is as high as 84 g / L, so it is suitable for the formulation of wastewater agglutinating agent. Item treatment After the first replacement After the second replacement After sulfuric acid (N) 2.2 1.8 0.1 Copper (g / L) 25 0.8 3.4ppm Iron (g / L) 0 25 84 Table (3) 15 200412330 [Simplified description of the diagram] (a The first part of the diagram is a flowchart of the method of the present invention. (II) Symbols of component A Purification B Primary replacement C Second replacement D Stabilization E Magnetic separation 16