553906 A7 _______B7 _ 五、發明說明（/ ) 發明領域 本發明係關於一種用於電子工業製程中，例如印刷電 路板或導線架之剝錫或剝錫鉛廢液的處理方法。更定而言 之，本發明係關於一種處理剝錫或剝錫鉛廢液以回收金屬 銅、金屬錫及金屬鉛之方法。 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銅之保護層。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 鑛錫或錫鉛層剝除，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1〇〇 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到15 g/L銅離子、1到40 g/L鐵離子或 亞鐵離子、10到Π0 g/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 錫或氫氧化錫沈澱析出，因此有時廢液中的亞錫離子含量 會低於10 g/L)、0到55 g/L亞鉛離子或鉛離子及2.0到 6·〇 N游離硝酸，因此有必要妥善處理剝錫鉛廢液，以避 免造成嚴重的環境污染。 目前習用的處理方法爲運用酸鹼中和原理，例如添加 氫氧化鈉中和剝錫鉛廢液中所含游離硝酸並調整ρΗ値至 8到13 ’使大部份重金屬陽離子形成氧化物或氫氧化物沈 ---------4_ 私紙張尺度適用中國國家標準（CNS)A4規格（21() χ 297公麓） " --------------------ιτ--^--------M —^wi (請先閱讀背面之注意事項再填寫本頁) 553906 A7 _____ B7___ 五、發明說明〇 ) 澱物，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，而濾液則利用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17791 1 ，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、沈澱劑及還原劑的方法，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，但類似於前面所提及之習用技術，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雜之缺 點，並不適用於處理剝錫鉛廢液。再者，在美國專利第 5766440 號標題爲”Method for Treating Sludge Precipitated in a Plating Bath Containing Haloid Ions”、第 61 10349 號標 題爲 ” Method for Recovering Metallic Tin from Electroplating Sludge”及中華民國專利公告號387948標 題爲「含錫淤渣的處理方法」中，則敘及將電鎮錫液內沈 澱的錫泥以強鹼溶解後，再電解還原成金屬錫的方法，由 於本發明技術處理剝錫鉛廢液過程中所產生的錫與鉛之氧 化物及氫氧化物沉澱物與電鍍錫液內沉澱的錫泥物化性質 類似，故將其關於處理錫泥的內容併入本文爲參考。 有鑑於此，需要一種具有經濟性、處理方式簡單，且 ___5 _ 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂 — -'--------線 (請先閱讀背面之注意事項再填寫本頁) 553906 A7 ______ 五、發明說明（） 可有效回收廢液中所含金屬離子的剝錫鉛廢液處理方法。 發明摘述 因此，本發明之目的爲提供一種處理剝錫或剝錫鉛廢 液以回收金屬銅、錫與鉛的方法，其包括： ⑴在高溫下藉由通氣氧化或化學氧化方法，將亞錫離 子與亞鉛離子氧化成爲錫與鉛之氧化物及氫氧化物沉澱 物； (ii) 固液分離步驟⑴中的錫與鉛之氧化物與氫氧化物 沉澱物； (iii) 將步驟(H)所得之固態錫與鉛之氧化物與氫氧化物 溶於強鹼或強酸中， (iv) 於高溫下電解還原於步驟(iii)所得之含錫與鉛之鹼 性溶液或酸性溶液，以回收製得金屬錫與金屬鉛；及 (v) 將步驟(Π)所產生之濾液於低溫下進行電解還原， 以還原銅離子爲金屬銅。 、 此外，根據本發明之方法亦具有另一優點爲經處理後 之剝錫或剝錫鉛廢液可適用於再配製成新鮮剝錫或剝錫鉛 液。 圖式簡單說明 圖1爲根據本發明之方法處理剝錫或剝錫鉛廢液之流 程方塊圖。 6 参紙張尺度適用中國國家標準（CNS)A4規格（21G X 297公爱) ' (請先閱讀背面之注意事項再填寫本頁) C________________. 553906 A7 ^___ B7___ 五、發明說明（j ) 發明詳述 根據本發明之處理剝錫或剝錫鉛廢液之方法主要是利 用高溫氧化與電解還原之方法來進行。 根據本發明之方法，在高溫下氧化生成錫與鉛之氧化 物及氫氧化物沉澱物之步驟⑴是在45到120°C的溫度範圍 內進行，較佳是在80到l〇5°C的溫度範圍內進行，因爲在 低於45°C進行氧化作用時則沉澱物之生成速率太慢，而在 高於120°C進行氧化作用時則會有大量硝酸被蒸發出來或 劇烈產生氮氧化物(NOx)揮發物之危險。因此，在45到 120°C的溫度範圍內，較佳是在80到105°C的溫度範圍內 進行步驟⑴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 化物及氫氧化物沈澱物之優點。 在步驟⑴中，可以單獨使用通氣氧化方法或化學氧化 方法，亦可合倂使用以提高氧化效果。該通氣氧化方法是 將氧氣或空氣通入廢液中。而該化學氧化方法是對廢液進 行蒸發濃縮來提高廢液中硝酸濃度、或直接添加濃硝酸到 廢液中。 在將氧氣或空氣通入廢液之例中，因爲氧分子在高溫 下可以快速氧化亞錫離子與亞鉛離子成爲錫與鉛之氧化物 及氫氧化物沉澱物，因此溶液中亞鉛離子及亞錫離子之濃 度會被快速降低。例如在8〇°C的溫度下，通入氧氣1小時 ，即可使廢液中的亞錫離子濃度降低至5 g/L以下。 在對廢液進行蒸發濃縮或直接添加濃硝酸到廢液之例 __7_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 553906 A7 ____B7_____ 五、發明說明（^ ) 中，因爲廢液中硝酸濃度提高，硝酸在高溫下可以快速氧 化亞錫離子與亞鉛離子形成錫與鉛之氧化物及氫氧化物沈 澱物。例如在80°C的溫度下，提高廢液中硝酸濃度至7 N 以上，即可使廢液中的亞錫離子濃度降低至5 g/L以下。 對廢液進行蒸發濃縮之方法可以在真空、常壓或加壓的條 件下進行，而適合用於直接添加到廢液中之濃硝酸可以是 濃度爲53%、58%、63%或98%之硝酸，較佳爲98%濃 硝酸。 視需要地，在步驟⑴中，若高溫氧化廢液中亞鉛離子 爲四價鉛離子的效率較低時，可於高溫氧化期間或之後， 於廢液中添加接近於鉛離子當量的硫酸根離子以促進形成 硫酸鉛晶體而沈澱析出。可利用之含硫酸根離子的化合物 包括，但不限定爲：硫酸、硫酸鈉或硫酸鉀等。 根據本發明之方法，在步驟(ii)中，可利用任何習知之 固液分離方法來從廢液中分離出錫與鉛之氧化物及氫氧化 物、以及視情況需要而產生之硫酸鉛沉澱物。 然後，在步驟(iii)中，將於步驟(ii)中所得之固態錫與 鉛之氧化物及氫氧化物以及硫酸鉛溶於強鹼或強酸中。可 使用之強鹼包括，但不限定於：氫氧化鈉、氫氧化鉀或其 混合物。較佳爲鹼當量濃度介於2.0到7·0Ν之氫氧化鈉、 氫氧化鉀或其混合溶液。另外，可使用之強酸則包括，但 不限定於：硫酸、鹽酸或其混合物。在步驟（出)中，所使 用之溶解溫度在室溫到180°C之間，較佳在8〇°C到16〇°C 之間。而溶解所需要之時間爲高於1小時，較佳爲高於5 ----------8____ — 一 才、紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I --------訂--------- (請先閱讀背面之注意事項再填寫本頁) 553906 A7 __ ___B7____ 五、發明說明（（） / 小時。如此可使溶液中的錫含量達到3〇 g/L以上，通常可 達50到150 g/L之間。 接著，在步驟（iv)中，將含錫與鉛之鹼性或酸性溶液 ，於50到105°C的高溫下進行電解還原步驟，可回收製得 金屬錫與金屬鉛，而陰陽極電位差則以介於u到7·〇ν之 間爲較佳。在步驟(W)期間，當溶液中錫含量低於5 g/L時 ，可將溶液迴流並再用於溶解固態錫與鉛之氧化物及氫氧 化物。至於回收得到之金屬錫與金屬鉛，可於硫酸亞錫溶 液中更進一步被電解精製以製得高純度錫，而其方法與習 用電解精製粗銅成爲精銅者相同。 於步驟(ii)所產生之濾液可於-5到40°C的低溫下進行 電解還原，將濾液中的銅離子還原成金屬銅，在低溫下進 行電解還原銅離子成爲金屬銅之步驟(v)具有抑制電解還原 氫離子爲氫氣及硝酸根離子爲氮氧化物(NOx)的效果，因 此可有效地電解還原銅離子爲金屬銅。在電解還原步驟(v) 中，陰陽極的電位差以介於1到5 V之間爲較佳。 剝錫鉛廢液在經由上述高溫氧化與低溫電解還原處理 步驟之後，可有效降低廢液中所含銅離子、亞錫離子及亞 鉛離子的濃度分別至1 g/L、5 g/L及1 g/L以下，而適用 於再配製成新鮮剝錫鉛液。 爲使更淸楚本發明技術的優點’兹以貫施例說明如下 實施例1 取5 L剝錫鉛廢液，該廢液內含約10 g/L Cu2+、30 _______ 9 衣紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） --------tr---------線 (請先閱讀背面之注意事項再填寫本頁) 553906 A7 _____B7 _ 五、發明說明（，L.) g/L Fe2+/Fe3+、30 g/L Sn2+及 10 ppm Pb2+。將該廢液加熱 至8(TC，攪拌並通入氧氣2小時後，廢液中形成大量錫之 氧化物及氫氧化物沈澱物。過濾分離錫之氧化物及氫氧化 物沉澱物。在80°C下，將所得之固態錫之氧化物及氫氧化 物溶於2 L濃度爲3 N的氫氧化鈉溶液中歷時6小時。接 著，提升此含錫鹼溶液溫度至95°C，並於陰陽極電位差爲 3.0 V的條件下進行高溫電解還原步驟歷時10小時後，溶 液中錫含量爲約3 g/L，並回收得到約120 g金屬錫。而分 離錫之氧化物及氫氧化物後所產生的濾液，則於15°C低溫 下進行電解還原步驟，其中陰陽極電位差保持在3.0 V， 持續電解至濾液中銅離子濃度低於1 g/L爲止。經處理後 剝錫鉛廢液內含約 1.0 g/L Cu2+、35.0 g/L Fe2+/Fe3+、3·0 g/L Sn2+及12 ppm Pb2+，因此適用於再配製成新鮮剝錫鉛 液。 實施例2 取 1 m3 內含約 5 g/L Cu2+、30 g/L Fe2+/Fe3+、30 g/L Sn2+及10 ppm Pb2+離子之剝錫鉛廢液，將該廢液加熱至90 °C，攪拌並通入氧氣2小時後，廢液中形成大量錫之氧化 物及氫氧化物沈澱物。在廢液溫度降低到50°C&T時’過 濾分離錫之氧化物及氫氧化物沉澱物。於100°CT ’將所 得之固態錫之氧化物及氫氧化物溶於300 L濃度爲3 N的 氫氧化鉀溶液中歷時1〇小時。然後’過濾去除溶液中尙 未溶解之固形物。隨後，調整此含錫驗溶液溫度至90°C ’ 於陰陽極電位差爲3.0 V的條件下進行高溫電解還原步驟 ____ίο ______ 衣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再填寫本頁)553906 A7 _______B7 _ 5. Description of the Invention (/) Field of the Invention The present invention relates to a method for treating tin stripping or tin-lead waste liquid used in the process of the electronics industry, such as printed circuit boards or lead frames. More specifically, the present invention relates to a method for treating tin stripping or tin stripping waste liquid to recover metallic copper, metallic tin, and metallic lead. Description of the prior art In the manufacturing process of general printed circuit boards, it is often necessary to plate tin or tin-lead on the copper layer as a protective layer for alkaline etching of copper. After the copper layer of the non-circuit part is etched and removed, the smelting tin or tin-lead layer is usually stripped with a nitric acid-based tin-lead solution to make the copper circuit appear. The main components of the lead stripping solution of nitric acid series are nitric acid and iron nitrate. During the process of tin stripping or tin stripping, 'when the free nitric acid content in the solution is lower than 4N or the tin content is higher than 100 g / L, That is, it must be replaced with a new liquid, thereby forming a tin-lead waste liquid. As the tin-lead waste liquid contains 2 to 15 g / L copper ions, 1 to 40 g / L iron ions or ferrous ions, 10 to Π0 g / L stannous ions or tin ions (when the waste liquid is stored or transported) During the process, stannous ions are oxidized to tin ions and precipitated out of tin oxide or tin hydroxide, so the content of stannous ions in the waste liquid may be less than 10 g / L), 0 to 55 g / L Lead ions or lead ions and 2.0 to 6.0 N free nitric acid, it is necessary to properly dispose of tin-lead waste liquid to avoid causing serious environmental pollution. The current conventional treatment method is to use the principle of acid-base neutralization, such as adding sodium hydroxide to neutralize the free nitric acid contained in the stripped tin and lead waste liquid and adjusting ρΗ 値 to 8 to 13 'so that most heavy metal cations form oxides or hydrogen. Oxide sink --------- 4_ Private paper size applies to China National Standard (CNS) A4 specifications (21 () χ 297 feet) " -------------- ------ ιτ-^ -------- M — ^ wi (Please read the notes on the back before filling out this page) 553906 A7 _____ B7___ V. Description of the invention 〇) The precipitate, filtered The oxide or hydroxide solid is refined by metallurgical tin, and the filtrate is crystallized by evaporation to make sodium nitrate crystals. However, the disadvantages of this conventional technique are that it consumes a large amount of sodium hydroxide and the sodium nitrate crystals obtained by crystallization are not commercially available. In the Republic of China Patent Bulletin No. 17791 1 titled "Method for Recovery of Metal Tin from Waste Tin Stripping Liquid", it teaches the use of methods of adding a neutralizing agent, precipitating agent and reducing agent to make the treated discharged water meet environmental protection standards. And make the stannous ions or tin ions in the waste liquid 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 Sexual approach. 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 to recover recycled tin plating additives and The method of metal tin, however, has the disadvantage that the treatment process is quite complicated, and is not suitable for the treatment of tin-lead waste liquid. Furthermore, U.S. Patent No. 5,676,440 is entitled "Method for Treating Sludge Precipitated in a Plating Bath Containing Haloid Ions", No. 61 10349 is titled "Method for Recovering Metallic Tin from Electroplating Sludge", and the Republic of China Patent Publication No. 387948 In the "treatment method of tin-containing sludge", the method of dissolving the tin sludge precipitated in the electric ballast tin solution with a strong alkali and then electrolytically reducing it to metallic tin is described. Because the technology of the present invention treats the tin-lead waste liquid The oxide and hydroxide precipitates of tin and lead produced in the process are similar in physicochemical properties to the tin sludge precipitated in the electroplating tin bath. Therefore, the content of tin sludge treatment is incorporated herein by reference. In view of this, there is a need for an economical, simple processing method, and _5 _ wood paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) ------------- ------- Order— -'-------- line (please read the precautions on the back before filling this page) 553906 A7 ______ V. Description of the invention () Can effectively recover the waste liquid Treatment method of tin-lead waste liquid from metal ions. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for treating tin stripping or tin stripping waste liquid to recover metallic copper, tin and lead, including: Oxidation of tin ions and lead ions into tin and lead oxides and hydroxide precipitates; (ii) tin and lead oxide and hydroxide precipitates in the solid-liquid separation step (i); (iii) step ( H) The obtained solid tin and lead oxides and hydroxides are dissolved in a strong base or strong acid, (iv) electrolytic reduction at high temperature in an alkaline or acid solution containing tin and lead obtained in step (iii), Metal tin and metal lead are prepared by recycling; and (v) the filtrate produced in step (Π) is electrolytically reduced at a low temperature to reduce copper ions to metal copper. In addition, the method according to the present invention also has another advantage that the treated tin stripping or tin stripping waste liquid can be adapted to be reconstituted into fresh tin stripping or tin stripping lead liquid. Brief Description of the Drawings Figure 1 is a block diagram of a process for treating tin stripping or tin stripping waste liquid according to the method of the present invention. 6 Reference paper size applies Chinese National Standard (CNS) A4 specification (21G X 297 public love) '(Please read the precautions on the back before filling this page) C________________. 553906 A7 ^ ___ B7___ 5. Description of the invention (j) Details of the invention The method for treating the stripped tin or stripped tin waste liquid according to the present invention is mainly carried out by a method of high temperature oxidation and electrolytic reduction. According to the method of the present invention, the step of oxidizing to form tin and lead oxides and hydroxide precipitates at a high temperature is performed in a temperature range of 45 to 120 ° C, preferably 80 to 105 ° C. Temperature range, because the precipitation rate is too slow when the oxidation is below 45 ° C, and a large amount of nitric acid is evaporated or the nitrogen is oxidized violently when the oxidation is performed above 120 ° C. Of volatile matter (NOx). Therefore, the step is performed in a temperature range of 45 to 120 ° C, preferably in a temperature range of 80 to 105 ° C. It has a rapid oxidation of stannous ions and lead ions in the waste liquid to tetravalent tin ions and four The effect of valence lead ions and the rapid formation of tin and lead oxide and hydroxide precipitates. In step (i), aeration oxidation method or chemical oxidation method may be used alone or in combination to improve the oxidation effect. The aeration oxidation method is to pass oxygen or air into the waste liquid. The chemical oxidation method is to evaporate and concentrate the waste liquid to increase the nitric acid concentration in the waste liquid, or directly add concentrated nitric acid to the waste liquid. In the case of passing oxygen or air into the waste liquid, oxygen molecules can rapidly oxidize stannous ions and lead ions to form oxides and hydroxides of tin and lead at high temperature. Therefore, lead ions and The concentration of stannous ions is rapidly reduced. For example, at 80 ° C for 1 hour, oxygen concentration can reduce the stannous ion concentration in the waste liquid to less than 5 g / L. In the case of evaporating and concentrating the waste liquid or directly adding concentrated nitric acid to the waste liquid __7_ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ -------- Order --------- line (please read the precautions on the back before filling this page) 553906 A7 ____B7_____ 5. In the description of the invention (^), because the nitric acid concentration in the waste liquid Improved, nitric acid can rapidly oxidize stannous ions and lead ions to form oxides and hydroxide precipitates of tin and lead at high temperatures. For example, at a temperature of 80 ° C, increasing the nitric acid concentration in the waste liquid to more than 7 N can reduce the stannous ion concentration in the waste liquid to less than 5 g / L. The method of evaporating and concentrating the waste liquid can be carried out under vacuum, atmospheric pressure or pressure. The concentrated nitric acid suitable for directly adding to the waste liquid can be 53%, 58%, 63%, or 98%. Nitric acid is preferably 98% concentrated nitric acid. Optionally, in step ⑴, if the efficiency of the lead ions in the high temperature oxidation waste liquid is tetravalent lead ions, it is possible to add sulfates close to the lead ion equivalent to the waste liquid during or after the high temperature oxidation. Ions are precipitated to promote the formation of lead sulfate crystals. The available sulfate ion-containing compounds include, but are not limited to, sulfuric acid, sodium sulfate, or potassium sulfate. According to the method of the present invention, in step (ii), any conventional solid-liquid separation method can be used to separate tin and lead oxides and hydroxides from the waste liquid, and lead sulfate precipitation as required Thing. Then, in step (iii), the solid tin and lead oxides and hydroxides and lead sulfate obtained in step (ii) are dissolved in a strong base or a strong acid. Strong bases that can be used include, but are not limited to, sodium hydroxide, potassium hydroxide, or mixtures thereof. Preferred is sodium hydroxide, potassium hydroxide or a mixed solution thereof having an alkali equivalent concentration of 2.0 to 7.0N. In addition, strong acids that can be used include, but are not limited to, sulfuric acid, hydrochloric acid, or mixtures thereof. In the step (out), the dissolution temperature used is between room temperature and 180 ° C, preferably between 80 ° C and 160 ° C. The time required for dissolution is higher than 1 hour, preferably higher than 5 ---------- 8____ — Only once, the paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) ) I -------- Order --------- (Please read the notes on the back before filling out this page) 553906 A7 __ ___B7____ 5. Description of the invention (() / hour. This will enable The tin content in the solution is more than 30 g / L, usually between 50 and 150 g / L. Next, in step (iv), the alkaline or acidic solution containing tin and lead is adjusted to 50 to 105 When the electrolytic reduction step is performed at a high temperature of ° C, metal tin and metal lead can be recovered, and the potential difference between the cathode and the anode is preferably between u and 7 · 〇ν. During step (W), when the When the tin content is less than 5 g / L, the solution can be refluxed and reused to dissolve the solid tin and lead oxides and hydroxides. As for the recovered metal tin and metal lead, it can be further taken in the stannous sulfate solution It is electrolytically refined to obtain high-purity tin, and the method is the same as that of conventional electrolytically refined crude copper to become refined copper. The filtrate produced in step (ii) can be -5 to 40 ° Step C of performing electrolytic reduction at a low temperature to reduce copper ions in the filtrate to metallic copper and electrolytic reduction of copper ions to metallic copper at a low temperature (v) has the ability to inhibit electrolytic reduction of hydrogen ions to hydrogen and nitrate ions to nitrogen oxidation (NOx) effect, so it can effectively electrolytically reduce copper ions to metallic copper. In the electrolytic reduction step (v), the potential difference between the cathode and anode is preferably between 1 and 5 V. Tin-lead waste liquid After the above high temperature oxidation and low temperature electrolytic reduction treatment steps, the concentration of copper ions, stannous ions, and lead ions in the waste liquid can be effectively reduced to 1 g / L, 5 g / L, and 1 g / L or less, respectively. In order to make it more clear, the advantages of the technology of the present invention are described in the following examples. Example 1 Take 5 L of tin-lead waste liquid, the waste liquid contains about 10 g / L Cu2 +, 30 _______ 9 Applicable paper size for China National Standard (CNS) A4 (210 χ 297 mm) -------- tr --------- line (please first Read the notes on the back and fill in this page) 553906 A7 _____B7 _ 5. Description of the invention (, L.) g / L Fe2 + / Fe3 +, 30 g / L Sn2 + and 10 ppm Pb2 +. After heating the waste liquid to 8 ° C, stirring and passing in oxygen for 2 hours, a large amount of tin oxide and hydroxide precipitates were formed in the waste liquid. The tin oxide was separated by filtration. And hydroxide precipitates. The obtained solid tin oxides and hydroxides were dissolved in 2 L of 3 N sodium hydroxide solution at 80 ° C for 6 hours. Then, the tin-containing alkali was raised. After the solution temperature reached 95 ° C, and the high-temperature electrolytic reduction step was performed under the condition that the potential difference between the anode and the anode was 3.0 V, after 10 hours, the tin content in the solution was about 3 g / L, and about 120 g of metal tin was recovered. The filtrate produced after the separation of tin oxides and hydroxides is subjected to an electrolytic reduction step at a low temperature of 15 ° C. The potential difference between the cathode and anode is maintained at 3.0 V, and the electrolysis is continued until the copper ion concentration in the filtrate is less than 1 g / So far. The treated tin-lead waste liquid contains approximately 1.0 g / L Cu2 +, 35.0 g / L Fe2 + / Fe3 +, 3.0 g / L Sn2 +, and 12 ppm Pb2 +, so it is suitable for re-formulation into fresh tin-lead solution. Example 2 Take 1 m3 of tin-lead waste liquid containing about 5 g / L Cu2 +, 30 g / L Fe2 + / Fe3 +, 30 g / L Sn2 +, and 10 ppm Pb2 + ions, and heat the waste liquid to 90 ° C. After stirring and passing in oxygen for 2 hours, a large amount of tin oxide and hydroxide precipitates were formed in the waste liquid. When the temperature of the waste liquid is lowered to 50 ° C & T ', the oxide and hydroxide precipitates of tin are separated by filtration. The obtained solid tin oxide and hydroxide were dissolved in 300 L of a 3 N potassium hydroxide solution at 100 ° CT 'for 10 hours. Then, the solution was filtered to remove undissolved solids. Subsequently, the temperature of the tin-containing test solution was adjusted to 90 ° C, and the high-temperature electrolytic reduction step was performed under the condition that the potential difference between the anode and the anode was 3.0 V. ____ ίο ______ The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm ) (Please read the notes on the back before filling this page)
n n flu I n I —ϋ 一：口、 i^— n m I n HI I 553906 A7 ____B7 _ 五、發明說明（^ ) 歷時約10小時後，此時溶液中錫含量低於5g/L，並回收 得到約23kg金屬錫。而分離錫之氧化物及氫氧化物後所 產生的濾液，則於15°C低溫下進行電解還原步驟，其中陰 陽極電位差保持在3 · 0 V，持續電解至爐液中銅離子含量 低於1 g/L爲止，而經處理後剝錫鉛廢液含約1.〇 g/L 、33.0 g/L Fe2+/Fe3+、5.0 g/L Sn2+及 11 ppm Pb2+，因此適 用於再配製成新鮮剝錫鉛液。 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，熟悉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。 才、紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)nn flu I n I —ϋ I: mouth, i ^ — nm I n HI I 553906 A7 ____B7 _ 5. Description of the invention (^) After about 10 hours, the tin content in the solution is lower than 5g / L and recovered About 23 kg of metal tin was obtained. The filtrate produced after the separation of the oxides and hydroxides of tin is subjected to an electrolytic reduction step at a low temperature of 15 ° C. The potential difference between the cathode and anode is maintained at 3.0 V, and the electrolysis is continued until the copper ion content in the furnace liquid is lower than Up to 1 g / L, and the treated tin-lead waste liquid contains about 1.0 g / L, 33.0 g / L Fe2 + / Fe3 +, 5.0 g / L Sn2 +, and 11 ppm Pb2 +, so it is suitable for re-formulation Peeling tin and lead. 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 based on the understanding of the present invention, and these modifications and changes should be It is included in the scope of patent application in this case. The paper and paper size apply the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling this page)
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