1227217 A? ____ B7 ____ 五、發明說明（） L發明領域 本發明係關於一種用於電子工業製程中，例如導線架 或印刷電路板之剝錫或剝錫鉛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剝錫或剝錫鉛廢液中銅· 、亞錫及亞鉛離子之方法。 2.先前技藝說明 在一般印刷電路板的製造過程中，常常需要在銅層上 電鍍錫或錫鉛以作爲鹼性蝕刻之保護層。當非線路部份之 銅層被蝕刻去除之後，通常以硝酸系列之剝錫鉛液將電鍍 錫或錫鉛層剝除，以使銅線路顯現出來。硝酸系列之剝錫 鉛液之主要成份爲硝酸及硝酸鐵，在剝錫或剝錫鉛過程中· •，當溶液中的游離硝酸含量低於4N或含錫量高於l〇〇g/L 時，即須以新液置換，因而形成剝錫鉛廢液。由於剝錫鉛 廢液中含有2-15g/L銅離子、l-40g/L鐵離子或亞鐵離子、 10-120g/L亞錫離子或錫離子（當廢液於儲存或運送過程中 ，亞錫離子會被氧化成錫離子並形成氧化錫或氫氧化錫沉 澱析出，因此有時廢液中的亞錫離子含量會低於l〇g/L)、 〇-5g/L亞鉛離子或鉛離子及2.0-6.ON游離硝酸，因此，有 必要妥善處理剝錫鉛廢液以避免造成環境污染。 . 目前習用的處理方法爲利用添加氫氧化鈉中和剝錫鉛 廢液中所含的游離硝酸，調整pH値至8-13使大部份重金 屬陽離子形成氧化物或氫氧化物沉殿析出，過濾所得氧化 物或氫氧化物固體，再以冶煉方法煉製金屬錫，而濾液則 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項寫本頁) --------訂-------- 1227217 A7 ------ ---B7__—_ 五、發明說明（） /經蒸發結晶以製成硝酸鈉晶體。然而，此習用技術之缺點 爲須耗用大量氫氧化鈉並且結晶所得硝酸鈉晶體不具商用 價値。於中華民國專利公告號177911，標題爲「從剝錫廢 '液回收金屬錫之方法」中，其教導利用添加中和劑、沉澱 劑及還原劑的方式，使處理後的排放水達到環保標準並使 廢液中的亞錫離子或錫離子還原成金屬錫而回收，但類似 於前面所提過之習用技術，該處理方法仍須耗用大量中和 劑及還原劑，因此爲不具經濟性的處理方法。另於中華民 國專利公告號258758，標題爲「鍍錫液之回收再生方法及 裝置」中，其說明利用離子交換樹脂以分離鍍液中鐵、鉻 、錫等離子，以回收再生鍍錫助劑及金屬錫的方法，然而 ’該方法具有處理過程相當繁雑之缺點，並不適用於處理 剝録給廢液。 3·發明摘述 因此’本發明之目的爲提供一種去除剝錫或剝錫錯廢 液中銅、亞錫及亞鉛離子之方法，不須耗用大量的中和劑 時亦不會有氮氧化物產生之困擾。 4.®式簡單說明 圖1爲根據本發明之方法處理剝錫鉛廢液之流程方塊 ® ’其中虛線方塊表示可視情況需要增加的步驟。 5·發明詳述 本發明的技術主要是利用電解方法來處理剝錫鉛廢液 4 (請先閱讀背面之注意事項i寫本頁) --------訂---------. 本紙張尺度適用中國國家標準（CNS)A4規格(210 x 297公釐） 1227217 a7 ___B7 __ 五、發明說明（） ，其包括(1)在低溫下進行電解還原步驟，將銅離子還原成 金屬銅，及(11)利用陽離子交換膜隔離廢液與陰極，在高溫 下進行電解氧化步驟，將亞錫離子與亞鉛離子氧化成錫與 鉛之氧化物及氫氧化物，而將廢液中的銅離子、亞錫離子 與亞鉛離子去除，使得去除這些陽離子後的廢液適於再配 製成新鮮剝錫鉛液，而達成廢液完全資源化的目的。 在本發明之方法中，電解還原步驟是在-5-4(TC的低溫 下進行，如此具有抑制電解還原氫離子爲氫氣及硝酸根離 子(N0〇爲氮氧化物(NOx)的效果，且於愈低溫的情況下， 電解還原銅離子爲金屬銅的效率越高，但以不發生結冰的 情況下爲原則，並且電解還原過程中陰陽極的電位差以介 於MV之間爲較佳；再者，電解氧化反應是在45-100°C的 高溫下進行，如此具有快速將廢液中亞錫離子與亞鉛離子 氧化成四價錫離子與四價鉛離子之功效，並迅速形成錫與. 鉛之氧化物及氫氧化物以沉澱析出，然後再利用任何固液 分離方法將沉澱物分離。在前述電解氧化步驟中，若所使 用之溫度越高，則電解氧化的效果越佳。再者，利用陽離 子交換膜隔離廢液與陰極，可避免廢液與陰極直接接觸， 因爲若廢液與陰極直接接觸會導致廢液中的硝酸根離子 (NCV)容易被還原成氮氧化物(NOx)而揮發出來並使電解氧 化效率降低。在利用陽離子交換膜隔離廢液與陰極中是將 廢液置於陽極，並以稀硫酸液作爲陰極液。在隔膜電解氧 化過程中，陰陽極的電位差以介於2-10V之間爲佳。在本 發明之方法中，電解還原與隔膜電解氧化步驟並無一定之 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項i寫本頁) · I I I I I I I · I I I I — I I I · 1227217 A7 ________B7 ___ 五、發明說明（） 先後次序要求，亦可交替重複使用。如圖1所示之剝錫鉛 廢液處理流程方塊圖。 運用本發明技術可輕易將剝錫鉛廢液中大部份的銅離 子、亞錫離子及亞鉛離子除去，不須耗用大量的中和劑， 同時亦不會產生氮氧化物。利用電解還原步驟可將廢液中 之銅離子濃度降低至lg/L以下，而利用隔膜電解氧化步驟 可將廢液中之亞錫離子及亞鉛離子的濃度分別降低至l〇g/L 及lg/L以下，使得處理後的廢液適用於再配製成新鮮剝錫. 鈴液。爲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5〇〇mL剝錫鉛廢液，廢液中含有i3.3g/L銅離子， 37.9g/L亞錫離子及3.9g/L亞鉛離子，於15π下進行電解還 原步驟’陰陽極電位差爲3.0V，電流爲2.5-3.5Α，處理後 銅離子濃度降低至〇.58g/L。 實施例2 : 取實施例1中所得到的經電解還原步驟處理後的剝錫 鉛廢液250mL，於50°C下進行隔膜電解氧化步驟，陰陽極 電位差爲5.0V，電流爲0.8-1.6A，在14小時之後，亞錫離 子與亞鉛離子濃度分別降低至9.lg/L及3.8g/L。 實施例3 : 延續實施例2，在進行50小時隔膜電解氧化後，亞錫. 6 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項i寫本頁) 裝 1227217 A7 _B7_ 五、發明說明（） 離子與亞鉛離子濃度分別降低至0.55g/L及0.52g/L。 實施例4 : 請先閱讀背面之注意事項寫本頁) 延續實施例3，在進行70小時隔膜電解氧化後，亞錫 離子與亞鉛離子濃度分別降低至〇.24g/L及0.072g/L。 在上述實施例2-4，於整個隔膜電解氧化過程中，均 未見到氮氧化物明顯的產生。因此，利用陽離子交換膜隔 離廢液與陰極具有避免氮氧化物產生的優點。 以上實施例僅爲本發明技術的示範例子，其並非用來 限定本發明爲特定形式，熟習該項技術者在瞭解本發明之 後，可依此進行任何修飾或改變，而該等修飾與改變應包 括於本案申請專利範圍之範疇內。 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）1227217 A? ____ B7 ____ 5. Description of the invention (L) Field of the Invention The present invention relates to a resource treatment method for stripping tin or stripping tin waste liquid from lead frames or printed circuit boards used in the electronics industry process. More specifically, the present invention relates to a method for removing copper, stannous, and lead ions from a stripped tin or stripped lead waste liquid. 2. Description of previous technology In the manufacturing process of general printed circuit boards, it is often necessary to electroplate tin or tin-lead on the copper layer as a protective layer for alkaline etching. After the copper layer of the non-circuit part is etched and removed, the electroplated tin or tin-lead layer is usually stripped with a nitric acid stripping tin-lead solution to make the copper circuit appear. The main components of the tin-lead solution of nitric acid series are nitric acid and iron nitrate. During the process of tin stripping or tin-lead stripping, when the free nitric acid content in the solution is lower than 4N or the tin content is higher than 100 g / L At this time, it must be replaced with a new liquid, thus forming a tin-lead waste liquid. As the tin-lead waste liquid contains 2-15g / L copper ion, 1-40g / L iron ion or ferrous ion, 10-120g / L tin ion or tin ion (when the waste liquid is stored or transported, The stannous ions will be oxidized to tin ions and form a precipitate of tin oxide or tin hydroxide. Therefore, the content of stannous ions in the waste liquid may be less than 10g / L), 〇-5g / L lead ions, or Lead ions and 2.0-6.ON free nitric acid, therefore, it is necessary to properly dispose of tin-lead waste liquid to avoid environmental pollution. . The current conventional treatment method is to use the addition of sodium hydroxide to neutralize the free nitric acid contained in the stripped tin and lead waste liquid, and adjust the pH to 8-13 to make most of the heavy metal cations form oxides or hydroxides and precipitate. The obtained oxide or hydroxide solids are filtered, and then metal tin is refined by smelting method, and the filtrate is 3 paper sizes applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back first) (Write this page) -------- Order -------- 1227217 A7 ------ --- B7 __—_ V. Description of the invention () / Made by evaporation and crystallization to make sodium nitrate Crystal. However, the disadvantages of this conventional technique are that a large amount of sodium hydroxide is consumed and the sodium nitrate crystals obtained by crystallization are not commercially available. In the Republic of China Patent Bulletin No. 177911, titled "Method for Recovery of Metal Tin from Waste Tin Stripping Solution", it teaches the use of neutralizing agents, precipitants and reducing agents to make the treated discharged water meet environmental protection standards. The stannous ion or tin ion in the waste liquid is reduced to metal tin and recovered, but similar to the conventional technology mentioned above, this treatment method still requires a large amount of neutralizer and reducing agent, so it is not economical. Processing method. Also in the Republic of China Patent Bulletin No. 258758, titled "Recycling and Regeneration Method and Apparatus for Tin Plating Bath", it describes the use of ion exchange resins to separate iron, chromium, tin and other ions in the plating bath in order to recover recycled tin plating additives and The method of metal tin, however, 'this method has the disadvantage that the processing process is quite cumbersome and is not suitable for the treatment of stripping to waste liquid. 3. Abstract of the Invention Therefore, the object of the present invention is to provide a method for removing copper, stannous, and lead ions from the stripped or stripped tin waste liquid, without the need to consume a large amount of neutralizing agent and no nitrogen Difficulties of oxide generation. 4.®-style brief description Figure 1 shows the process block of processing tin-lead waste liquid according to the method of the invention. 5. · Detailed description of the invention The technology of the present invention mainly uses electrolytic method to dispose of tin-lead waste liquid 4 (please read the precautions on the back first to write this page) -------- Order ------ ---. This paper size is in accordance with China National Standard (CNS) A4 (210 x 297 mm) 1227217 a7 ___B7 __ 5. Description of the invention (), which includes (1) electrolytic reduction step at low temperature to remove copper ions Reduction to metallic copper, and (11) using a cation exchange membrane to separate the waste liquid from the cathode, and performing an electrolytic oxidation step at high temperature to oxidize stannous ions and lead ions to tin and lead oxides and hydroxides, and The removal of copper ions, stannous ions, and lead ions in the waste liquid makes the waste liquid after removing these cations suitable for reconstitution into a fresh tin stripping lead liquid, thereby achieving the purpose of completely recycling the waste liquid. In the method of the present invention, the electrolytic reduction step is performed at a low temperature of -5-4 (TC, so that it has the effect of inhibiting electrolytic reduction of hydrogen ions to hydrogen and nitrate ions (NO is nitrogen oxides (NOx), and At lower temperatures, the efficiency of electrolytic reduction of copper ions to metallic copper is higher, but on the principle that no icing occurs, and the potential difference between the anode and the cathode during electrolytic reduction is preferably between MV; In addition, the electrolytic oxidation reaction is performed at a high temperature of 45-100 ° C, so that it has the effect of rapidly oxidizing stannous ions and lead ions in the waste liquid into tetravalent tin ions and tetravalent lead ions, and quickly forms tin. And. Lead oxides and hydroxides are precipitated by precipitation, and then any solid-liquid separation method is used to separate the precipitates. In the foregoing electrolytic oxidation step, if the higher temperature is used, the effect of electrolytic oxidation is better. In addition, the use of a cation exchange membrane to separate the waste liquid from the cathode can avoid direct contact between the waste liquid and the cathode, because if the waste liquid is in direct contact with the cathode, the nitrate ion (NCV) in the waste liquid is easily reduced to nitrogen oxidation. (NOx) and volatilize and reduce the efficiency of electrolytic oxidation. When using a cation exchange membrane to separate the waste liquid from the cathode, the waste liquid is placed in the anode, and a dilute sulfuric acid solution is used as the cathode liquid. During the diaphragm electrolytic oxidation process, the cathode and anode The potential difference is preferably between 2-10V. In the method of the present invention, there are no certain 5 steps of electrolytic reduction and diaphragm electrolytic oxidation. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ) (Please read the precautions on the back to write this page first) · IIIIIII · IIII — III · 1227217 A7 ________B7 ___ 5. Description of the invention Block diagram of waste liquid treatment process. By applying the technology of the present invention, most of the copper ions, stannous ions, and lead ions in the stripped tin and lead waste liquid can be easily removed, without using a large amount of neutralizer, and without Generates nitrogen oxides. The concentration of copper ions in the waste liquid can be reduced to less than lg / L by using the electrolytic reduction step, and the stannous ions and lead ions in the waste liquid can be reduced by using the diaphragm electrolytic oxidation step. The concentration is reduced below 10g / L and lg / L, respectively, so that the treated waste liquid is suitable for re-formulation into fresh stripping tin. Bell liquid. To better understand the advantages of the technology of the present invention, the following examples are used to explain The following Example 1: Take 500mL tin stripping lead waste liquid, the waste liquid contains i3.3g / L copper ions, 37.9g / L stannous ions and 3.9g / L lead ions, electrolytic reduction at 15π Step 'The potential difference between the cathode and the anode is 3.0 V, the current is 2.5-3.5 A, and the copper ion concentration is reduced to 0.58 g / L after the treatment. Example 2: Take the stripped tin obtained in the electrolytic reduction step obtained in Example 1 250 mL of lead waste liquid was subjected to a diaphragm electrolytic oxidation step at 50 ° C. The potential difference between the cathode and anode was 5.0 V and the current was 0.8-1.6 A. After 14 hours, the concentrations of stannous ions and lead ions were reduced to 9.lg / L and 3.8g / L. Example 3: Continuing with Example 2, after 50 hours of diaphragm electrolytic oxidation, stannous tin. 6 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first (I write this page) Pack 1227217 A7 _B7_ 5. Description of the invention () The concentration of ions and lead ions are reduced to 0.55g / L and 0.52g / L, respectively. Example 4: Please read the notes on the back to write this page.) Continuing with Example 3, after 70 hours of diaphragm electrolytic oxidation, the concentrations of stannous ions and lead ions were reduced to 0.24 g / L and 0.072 g / L, respectively. . In Examples 2-4 mentioned above, no significant generation of nitrogen oxides was observed during the entire electrolytic oxidation process of the separator. Therefore, using a cation exchange membrane to separate the waste liquid from the cathode has the advantage of avoiding the generation of nitrogen oxides. The above embodiments are merely exemplary examples of the technology of the present invention, and are not intended to limit the present invention to a specific form. Those skilled in the art can make any modifications or changes in accordance with the present invention after understanding the invention, and these modifications and changes should be It is included in the scope of patent application in this case. 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)