200417626 玖、發明說明 【發明所屬之技術領域】 本發明係屬於一種剝錫鉛廢液之處理方法，其應用在 電子工業製程中，因剝離電鍍錫或電鍍錫鉛層所產生廢液 之處理方法。另外，本發明亦相關於一種可自剝離電鍵錫 或電鍍錫鉛的廢液中，回收金屬錫、金屬銅、硫酸銅、硫 酸亞鐵或硫酸鐵的方法。 【先前技術】 在一般印刷電路板的製造過程中，常常需要在銅層上 電鍍錫層或錫鉛層，以保護在鹼性蝕刻過程中的銅層。當 餘刻後去除非線路部份的銅層後’通常利用硝酸系的強酸 溶液將電鑛錫層或電鍍錫鉛層剝除，以便使銅層的線路部 份得以顯現。利用硝酸系的強酸溶液，來剝除電鍍錫層或 電鍵錫錯層的方法，可以參考美國專利公告號第5,911，9〇7 、5, 928, 529 、 5, 989, 449 、 6, 258, 294 B1 及 2001 /000731 7A號等前案，其中強酸溶液的主要成份為硝酸 與石肖酸鐵’在剝除電鍍錫層或電鍍錫鉛層的過程中，當溶 液中的游離硝酸根陰離子濃度低於4N，或含錫量高於 1 〇〇g/L時，即需重新配製更換新的硝酸系溶液，因而會產 生剝離電鎮錫層或電鐘錫叙F層的廢液。由於剝離電錢錫層 或電艘錫錯層的廢液中，含有2至15g/L的銅離子、丄至 4〇g/L的鐵離子或亞鐵離子、1〇至12〇g/L的錫離子或亞錫 離子（當廢液在儲存或運送的過程中，錫離子會被氧化形 成氧化錫或氫氧化錫沈澱物析出，因此有時候存在於廢液 200417626 200417626 )、0 至 55g/L 因此有必要妥善 ’以免嚴重污染 中的錫離子及亞錫離子含量會低於叫几。 的鉛離子及2.0至6.⑽的游離硝酸溶液， 處理經剝離電鑛錫層或電鑛錫錯層的廢液 環境。 a =中的游離硝酸’並調整ΡΗ值在…3之間，使：; 金屬陽離子形成氧化物或氫氧化物之沈㈣200417626 发明 Description of the invention [Technical field to which the invention belongs] The present invention belongs to a method for treating tin-lead waste liquid, which is applied in the process of the electronics industry, and is a method for treating waste liquid produced by peeling off electroplated tin or electroplated tin-lead layers. . In addition, the present invention also relates to a method for recovering metallic tin, metallic copper, copper sulfate, ferrous sulfate, or ferric sulfate from a waste liquid capable of self-stripping bond tin or electroplating tin-lead. [Previous technology] In the manufacturing process of general printed circuit boards, it is often necessary to plate a tin layer or a tin-lead layer on a copper layer to protect the copper layer during the alkaline etching process. When the copper layer of the non-circuit portion is removed after a while ', a strong acid solution of nitric acid is usually used to strip the electro-mineral tin layer or electroplated tin-lead layer so that the circuit portion of the copper layer can be visualized. For the method of stripping the electroplated tin layer or the bond tin layer by using a strong acid solution of nitric acid, refer to US Patent Publication Nos. 5,911,907, 5, 928, 529, 5, 989, 449, 6, 258, 294 B1 and 2001/000731 7A and other previous cases, in which the main components of the strong acid solution are nitric acid and iron iron carbonate. In the process of stripping the electroplated tin layer or electroplated tin-lead layer, the concentration of free nitrate anions in the solution When it is lower than 4N or when the tin content is higher than 1000 g / L, it is necessary to re-formulate and replace the new nitric acid solution, so the waste liquid that peels off the electrical ballast layer or the electrical layer tin layer F will be generated. The waste liquid that strips the tin layer or the tin layer of the electric boat contains 2 to 15 g / L of copper ions, rhenium to 40 g / L of iron ions or ferrous ions, and 10 to 120 g / L. Tin ions or stannous ions (when the waste liquid is stored or transported, tin ions will be oxidized to form tin oxide or tin hydroxide precipitates, so it sometimes exists in the waste liquid 200417626 200417626), 0 to 55g / L Therefore, it is necessary to properly 'in order to avoid the content of tin ions and stannous ions in severe pollution will be lower than a few. Of lead ions and free nitric acid solution of 2.0 to 6.⑽, to treat the waste liquid environment after stripping the tin layer or tin layer of the electric mine. a = free nitric acid ’and adjust the pΗ value between 3, so that :; metal cations form an oxide or hydroxide sink
;τ:化物或氯氧化物固形物，再以冶煉的方法練製： 法還度鹼液將固形物溶解後，再以電解的方 定原…屬錫’而遽液則利用蒸 :㈣體。然而習用技術之主要缺點為氧化 =中含有不少重金屬〜載及錯，特別是鋼;:： /口煉或電解所得金屬錫的純度。 曰 於中華民國專利法公告第177911辦「… 金屬錫之方法?φ 4 0攸剝錫廢液回收 中^ 中，揭露利用添加還原劑、沈殿劑及 置換σ=Γ去’使處理後的排放水達到環保標準並以銘片 加以：Γ的錫離子或亞錫離子，以將還原的金屬錫( /回收。然而，該專利内容中所閣述的處理方法，需耗 二劑及沈殿劑’且過程繁雜’故為不經濟之處 成氣化物Ρ 處理過程中’錫離子或亞锡離子極易形 成乳化物或氫氧化物沈澱析出，因一 銘片置換還原得金屬錫亦為其缺點。 適當時機以 =於中華民國專利公告第258758號「鑛錫液之回 法及裝置」乙案中，揭露利用離子交換樹脂以分 200417626 離電鍍液中的鐵、鉻、錫等離子之用以回收再生鍍錫助劑 及金屬錫的方法。然而該方法亦具有處理過程相當繁雜的 缺點，因此並不適用於處理剝離電鍍錫層與電鍍錫鉛層後 的廢液。 另外，中華民國專利公告第472030號「剝錫鉛廢液之 處理方法」乙案中，揭露於廢液中加入沈澱劑與中和劑（鹼 性藥劑），並進行過濾、加熱去氨、沈澱溶解等一連串分離 程序，以達到廢液中的有價成份的回收與廢液處理的環保 工作。該方法可由剝錫鉛廢液回收之成分製成95%純度之 錫酸鈉、80%之氟化鈉或硝酸鈉及93%之硫酸銅晶體。錫 酸鈉可經過電解精練而得到99·9%的金屬錫；氟化鈉或硝酸 鈉及硫酸銅，則可藉由再結晶的方式提高其純度。該方法 雖然可以達到廢液中有價成份之回收與廢液處理的環保工 作，但與前述習用技術具有相同的缺點，即中和後所產之 乳化物或風氧化物固形物中含有不少重金屬銅、鐵及錯， 特別是銅含量過高時會使得後續精製錫的程序變得過^繁 雜。 ’、 至於中華民國專利公告第387948號、美國專利公告身 576644G 611G349及6290835號等專利前案，則提及將屬 鑛錫液内所沈殿的錫泥或處理剝錫船廢液的過程中所❹ 的錫泥’卩強驗溶解後’再經電解還原得金屬錫的方法， 其可供作處理錫泥的參考。另外，與本發明人之中華民國 專利a σ第4981 1 2號「一種去除剝錫或剝錫鉛廢液中銅、 亞錫及亞鉛離子之方法」，其處理剝鉛廢液的内容亦可併 200417626 入作為參考。 【發明内容】 、處理方式簡單而完 子的剝錫鉛廢液處理 有鑑於此，需要一種具有經濟性 整，且可有效回收廢液中所含金屬離 方法。 ”、、’、 禋處理剝錫或剝錫錯巧 液以回收金相、金屬銅或硫_與硫酸亞鐵成硫酸鐵白 方法，其包括： ^匕步驟」在高溫下將錫離子與錯離子氧化成為錫、 金口之氧化物及氣氧化物沈澱物； 固液分離步驟：將氧化步驟 ^ 气汽儿m VW侍之錫、鉛之氧化物及 風氧化物沈;殿物加以固液分離； 還原步驟：將固液分離步驟所得之固態錫與鉛之氧化 物及虱虱化物還原成為金屬錫或錫鉛合金； 回收步驟··將固液分離 ，經過、清、r μ ι所屋生之濾液以碱"口後 应㈣车口严 合解卒取、電解還原、置換 反應專程序回收製得今屬 且 可達法除可確實達到廢液處理的目的，並 J貝/原凡全回收的效果。 【實施方式】 方去看第一圖所示，本發明處理剝錫或剝錫，廢、夜之 方法主要是利用高溫氧化、冶煉、^廢液之 結晶等方法來推 举逖原、中和及蒸發 氧化步驟、固液分離步驟、還原步驟及 200417626 回收步驟。 ”本發明方法之氧化步冑乃是在高溫下氧化生成錫與鉛 之氧化物及氫氧化物沈;殿之步驟，》45到12代的溫度範 圍内進行，較佳是在60至,！ 105t的溫度範圍内進行，因為 在低於45°C進行氧化作用時，沈殿物之生成速率太慢，而 在高於12Gt進行氧化作料，則會有大量錢被蒸發出來 或劇烈產生氮氧化物⑽χ)#揮發物之危險。因此，在仉 到，12〇t的溫度範圍内，較佳是在6〇 _ i〇rc的溫度範圍 内進行氧化步驟將具有快速將廢液中錫離子與敍離子氧化 形成錫與錯之氧化物及氫氧化物沈澱物之功效。 在氧化步驟中，可以單獨使用通氣氧化方法、化學氧 化方法或電解氧化方法，亦可合併使用以提高氧化效果。 ,:氣氧化方法疋將臭氧、氧氣或空氣等有助於氧化反應 進：之氣體直接通入廢液中；該化學氧化方法是對廢液進 行洛發濃縮來提高廢液切酸濃度或是直接添加濃墙酸到 :液中？該電解氧化方法是在電解槽中，對陰陽極施加 電位差使陽極區域發生氧化作用來進行。 在前述之通氣氧化方法中，因為氧分子在高溫下可以 快速氧化錫離子與錯離子，使之形成錫與錯之氧化物及氣 氧化物沈殿物’因此溶液中錫離子與錯離子之濃度會快速 降低。例如在帆的溫度下，通人氧41小時 液中的錫離子濃度降低至5g/L以下。 在前=之化學氧化方法中’因為廢液中石肖酸濃度會被 面’而石肖酸在高溫下可以快速氧化錫離子與錯離子，使 12 200417626 之形成錫與船之氧化物及氫氧化物沈澱物。例如在阶的 溫度下，提高廢液中石肖酸濃度至7N以上，即可使廢液中的 錫離子濃度降低至5g/L以下。該化學氧化方法可以在直空 、常壓或加壓的條件下進行，而直接添加到廢液中之濃硝 酸可以是濃度介於50〜1〇〇%之市售硝酸。 在前述之電解氧化方法中，陰陽極電位差係保持在2 到6V之間’猎由陽極區域的電解氧化作用，使得廢液 錫離子與鉛離子形成錫盘 " /取场兴鉛之虱化物及虱氧化物沈澱物。 例如在、陰陽極電位差4肩的條件下進行電解氧化* 小時’即可使廢液中錫離子濃度降低至5g/L以下。 視其需要，在氧化步驟中，若高溫氧化廢液中之㈣ 子形成錯之氧化物及氫氧化物沈澱物的效率過低時，可於 雨溫氧化期間或之後’於廢液中添加接近於鉛離子备 硫酸根離子以促進形成硫酸錯晶體而沈澱析出。其；里人 硫酸根離子的化合物& & 士 ^ 或硫酸卸等。㈣、硫酸鈉 本發明方法之固液分離步驟中，可利用任何習知 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 、並視情況需要進而產生硫酸錯沈殿物。相 ο華㈣專利公告號第47測號，以本發明方法m /、釔之氧化物及氫氧化物沈澱物中僅含微量銅、 鐵）離子，故德蜷、萝m止 丁次鐵（亞 八 故後、，"還原步驟較易製得高純度金屬錫或锡錯合 孟 〇 遌原^秫中，乃是將於固液分離步驟t分離所得之 13 200417626 固悲錫與鉛之氧化物及氫氧化物，以及可能產生之硫酸鉛 沈澱物，先以水洗淨及烘乾後，再與含碳成份為主的活性 石厌、焦碳或石墨以及碳酸鈉混合並研磨，於6〇〇到 高溫下，較佳800到1 000。(：，進行冶煉’可製得金屬錫或 錫鉛合金。或者先以水洗淨後，將沈澱物溶於強鹼中，可 使用的強鹼包括有，但不限定於：氫氧化鈉、氫氧化鉀或 其混合物。較佳的鹼為當量濃度介於2 〇到7 〇N之氫氧化 鈉、氫氧化鉀或其混合溶液，所使用的溶解溫度在室溫到 180°C之間，較佳在80它到16〇t之間，而溶解所需要之時 間為高於i小時，較佳為高於5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5〇到15〇g/L之間。渡 除未溶解的固形物後，將此含錫與鉛之鹼性溶液，於50到 5C的/里度下進行電解還原步驟，可回收製得金屬錫或錫 錯合金，而陰陽極電位差則以介於I 5到7 〇v之間為較佳 。以高溫冶丈東法或電解還原法所製得之金屬錫或錫鉛合金 ’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為精銅者相同。 二氧化步私同溫氧化後，剝錫鉛廢液中大部份錫離巧 與錯離子均已被氧化形成錫與錯之氧化物及氫氧化物沈调 物，再經固液分離步驟固液分離之後，渡液中僅含請 離子與錯離子，以及2至叫几的銅離子、丄至衝几的錯 離子或亞鐵離子與2.0至6.0N的游離硝酸。 、將固液分離步驟所產生之濾、液於回收步驟中以氫氧仆 鈉或氫氧化卸中和並調整其pH值至δ〜ΐ3，使濾、液中之鎖 200417626 及鋼等重金屬—π , '离離子形成氧化物及氫氧化物沈澱析出，再經 固液分離德，7 ~ A , 」侍含硝酸鈉或硝酸鉀的濾液與含鐵及銅等 氧化物及氣氧化物沈澱物的濾餅。所得濾液經加熱除氨後 可使用療發結晶方法製得硝酸鈉或硝酸鉀晶體，而濾餅 則經添加稀硫酸溶液溶解後，利用萃取法製得硫酸銅及硫 酉欠鐵或& ^亞鐵’或以置換法製得金屬銅粉末與硫酸亞鐵 ’亦或以電解還原法製得金屬銅粉末與硫酸亞鐵，亦或以 電解避原法製得金屬銅與硫酸亞鐵。前述之萃取法可參考 美國專利公告號第4, 252, 621號，中國大陸專利公告號第 1 154723A號及第1299784A號等，利用商標名為[ιχ_54的 有機萃取劑萃取稀硫酸溶液中的銅離子，再以濃硫酸溶液 反萃取溶於有機萃取劑ux—54之迴流，再利用於萃取稀硫 酸浴液中的銅離子，而硫酸銅溶液則經冷卻結晶或蒸發結 曰曰、過濾及乾燥等步驟製得硫酸銅晶體，過濾所產生的結 晶母液亦經迴流再用於反萃取有機萃取劑LIX—54中的銅離 子；前述之置換法為利用添加鐵粉於稀硫酸溶液中，以置 換溶液中之銅離子為金屬銅粉，而鐵粉則溶解形成亞鐵離 子’經過濾、乾燥製得金屬銅㉟，過濾所產生的硫酸亞鐵 溶液則經蒸發結晶製得硫酸亞鐵晶體，或以氧氣、空氣等 氧化形成硫酸鐵溶液；前述之電解還原法為將稀硫酸溶液 置於電解槽中，於陰陽極電位差丨至5v的條件下，將溶液 中的銅離子還原成金屬銅，殘餘硫酸亞鐵溶液則經蒸發結 晶製得硫酸亞鐵晶II，或以氧氣、空氣等氧化形成硫酸鐵 溶液。 15 200417626 【實施例] 實施例1 : 取5L剝錫鉛廢液，該廢液内含約1〇g/L Cu2+、3〇g/L Fe /Fe 、3〇g/L Sn2 + /Sn4 +及 10 ppm Pb2+。將該廢液加熱 至8〇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。過濾、分離錫之氧化物及氫氧化 物=澱物。在8(rc下，將所得之固態錫之氧化物及氯氧化 物/合於2L，濃度為3N的氫氧化鈉溶液中歷時6小時。接著 ，提昇此含錫鹼溶液溫度至95°C，並於陰陽極電位差為 3· 0V的條件下進行高溫電解還原步驟歷時1 〇小時後，溶液 中錫含量約3g/L，並回收得到約12叶金屬錫。 實施例2 : 、同實施例1的操作，於過濾分離錫之氧化物及氫氧化 物沈舨物後’將其經水洗及烘乾，取乾沈澱物，加 入2Og活性奴及80. 〇3g碳酸鈉，經混合及研磨後，於875 C高溫下歷時4小時，冶煉製得51. 2g純度為98. 5%的金屬 錫。 實施例3 :; τ: compounds or solids of chlorine oxides, and then smelted: after the solids are dissolved in the alkaline solution, and then electrolyzed, it is tin ... and the mash is steamed: carcass. However, the main disadvantage of the conventional technology is that oxidation = contains a lot of heavy metals ~ load and fault, especially steel; ::: purity of metal tin obtained by smelting or electrolysis. It was stated in the Patent Law of the Republic of China No. 177911, "... Method of metal tin? Φ 4 0 You stripping tin waste liquid recovery ^, revealed the use of reducing agents, Shen Dian agent and replacement σ = Γ to make the treated emissions Water meets environmental protection standards and is added on the nameplate: Γ tin ions or stannous ions to recover the reduced metal tin (/ recovery. However, the treatment method described in the patent content requires two agents and Shen Dian agent ' And the process is complicated, so it is uneconomical to form gaseous compounds. During the treatment process, tin ions or stannous ions can easily form emulsions or hydroxide precipitates. Metal tin is also a disadvantage due to the replacement of a nameplate. At the appropriate time, in the second case of the Republic of China Patent Bulletin No. 258758 "Return Method and Device for Mineral Tin Liquid", the use of ion exchange resin was disclosed to separate the 200417626 iron, chromium, tin and other ions in the plating solution for recycling. Tin plating aid and metal tin method. However, this method also has the disadvantage of a complicated process, so it is not suitable for the treatment of waste liquid after stripping the electroplated tin layer and the tin-lead layer. In addition, the Chinese people In the second case of Patent Bulletin No. 472030, "Method for Disposing of Tin-Lead Stripping Waste Liquid", it is disclosed that a precipitant and a neutralizing agent (basic agent) are added to the waste liquid, and a series of separations such as filtration, heating to remove ammonia, precipitation and dissolution are disclosed. Program to achieve the environmental protection work of recovering valuable components in waste liquid and treating waste liquid. This method can make 95% pure sodium stannate, 80% sodium fluoride or sodium nitrate from the components recovered from stripped tin lead waste liquid And 93% copper sulfate crystals. Sodium stannate can be electrolytically refined to obtain 99.9% metal tin; sodium fluoride or sodium nitrate and copper sulfate can be purified by recrystallization. Although this method It can achieve the environmental protection work of recovering valuable components in waste liquid and treating waste liquid, but it has the same shortcomings as the previous conventional technology, that is, the emulsified product produced after neutralization or the solid solid of wind oxide contains a lot of heavy metals copper and iron. Wrong, especially when the copper content is too high, the subsequent process of refining tin becomes too complicated. ', As for the pre-patent patents such as the Republic of China Patent Bulletin No. 387948, US Patent Bulletin Nos. 576644G, 611G349, and 6290835, etc. , It mentions the method of 'reducing the strength of the tin mud which was used in the process of disposing of the tin-stripping boat's waste liquid in the tin tin of the mine's tin hall', and then electrolytically reducing the tin to obtain tin. As a reference for the treatment of tin mud. In addition, with the inventor's Republic of China patent a σ No. 4981 12 "a method for removing copper, stannous and lead ions from waste tin stripping or stripping tin and lead waste", its treatment The content of lead stripping waste liquid can also be incorporated as a reference for 200417626. [Summary of the Invention] In view of this, a tin stripping lead waste liquid treatment with simple and complete processing is needed, and an economical and effective method can be used to recover the waste liquid. Containing metal ionization method. ",,,,,,,,,,,,,,,,,,,,,,,,, and sintered tin to remove metal or copper, or sulfur, and ferrous sulfate to form ferric sulfate white, which includes: The oxidation of tin ions and ions into tin, gold oxide and gas oxide deposits; solid-liquid separation step: oxidation step ^ gas vapor m VW tin, lead oxide and wind oxide precipitation ; Palace objects are solid-liquid separation; Reduction step: solid The solid tin and lead oxides and lice compounds obtained in the liquid separation step are reduced to metal tin or tin-lead alloys; the recovery step is to separate the solid and liquid, and the filtrate from the house after passing through the cleansing and r μm is treated with alkali " After the mouth, the car mouth should be closely integrated with the special procedures of extraction, electrolytic reduction, and replacement reaction to obtain the current genus and reachable removal, which can indeed achieve the purpose of waste liquid treatment, and J Bei / the original full recovery effect. [Embodiment] As shown in the first figure, the method of treating tin stripping or tin stripping, waste, and night in the present invention mainly uses high-temperature oxidation, smelting, and crystallization of waste liquid to recommend Liaoyuan, neutralization, and Evaporation oxidation step, solid-liquid separation step, reduction step and 200417626 recovery step. "The oxidation step of the method of the present invention is the oxidation at high temperature to form the oxides and hydroxides of tin and lead; the step of the temple," is performed within the temperature range of 45 to 12, preferably 60 to! The temperature range is 105t, because the oxidation rate of Shen Dianwu is too slow when the oxidation is performed below 45 ° C, and when the oxidation is performed above 12Gt, a lot of money is evaporated or nitrogen oxides are generated violently. ⑽χ) # The danger of volatiles. Therefore, performing the oxidation step in the temperature range of 120 ° t, preferably in the temperature range of 60 ° _rc, will have a rapid separation of tin ions The effect of ionic oxidation to form tin and copper oxides and hydroxide precipitates. In the oxidation step, aeration oxidation method, chemical oxidation method or electrolytic oxidation method can be used alone, or they can be used in combination to improve the oxidation effect. Oxidation method: Ozone, oxygen, or air is used to facilitate the oxidation reaction: the gas is directly passed into the waste liquid; the chemical oxidation method is to concentrate the waste liquid to increase the acid concentration of the waste liquid or directly add Concentrated wall acid to: in the liquid? The electrolytic oxidation method is performed in an electrolytic cell by applying a potential difference to the anode and the anode to oxidize the anode area. In the aforementioned aeration oxidation method, oxygen molecules can rapidly oxidize tin at high temperatures Ions and wrong ions, to form tin and wrong oxides and gas oxides Shen Dianwu ', so the concentration of tin ions and wrong ions in the solution will quickly decrease. For example, at the temperature of a sail, 41 hours of oxygen in the liquid The concentration of tin ions is reduced to less than 5g / L. In the previous chemical oxidation method, 'because the concentration of lithosolic acid in the waste liquid will be surfaced', and lithosolic acid can rapidly oxidize tin ions and mismatch ions at high temperatures, making 12 200417626 The formation of oxides and hydroxide precipitates of tin and ships. For example, at the temperature of the stage, increasing the concentration of lignosolic acid in the waste liquid to more than 7N can reduce the concentration of tin ions in the waste liquid to less than 5g / L. The The chemical oxidation method can be performed under the conditions of direct air, normal pressure or pressure, and the concentrated nitric acid directly added to the waste liquid can be a commercially available nitric acid with a concentration of 50 ~ 100%. In the chemical method, the potential difference between the anode and the anode is maintained between 2 and 6V. The electrolytic oxidation in the anode area causes the tin ions and lead ions in the waste liquid to form a tin plate. Precipitate. For example, electrolytic oxidation under the conditions of a potential difference of 4 anodes and 4 anodes can reduce the concentration of tin ions in the waste liquid to less than 5 g / L. If necessary, in the oxidation step, if the waste liquid is oxidized at high temperature, When the efficiency of the formation of the wrong oxides and hydroxide precipitates in the nuclei is too low, it is possible to add lead ions close to lead ions and sulfate ions to the waste liquid during or after the oxidation at rain temperature to promote the formation of sulfuric acid wrong crystals. Precipitation. Its compound of sulfate ion & & ^^ or sulfuric acid, etc. In the solid-liquid separation step of the method of the present invention, any conventional liquid separation method can be used to remove from the waste liquid. The oxides and hydroxides of tin and lead are separated, and if necessary, further sulfuric acid is produced. Phase ㈣ Huaxun Patent Bulletin No. 47 test number, according to the method of the present invention m /, yttrium oxide and hydroxide precipitates contain only trace amounts of copper and iron) ions, After Yaba ’s death, the " reduction step is easier to produce high-purity metal tin or tin complex Mengyuan ^ 秫, which is obtained by the solid-liquid separation step 13 200417626 Gu Bei tin and lead Oxides and hydroxides, as well as possible lead sulfate precipitates, are washed and dried with water, and then mixed with activated carbon containing carbon, activated carbon, graphite or sodium carbonate, and ground. From 600 to high temperature, preferably from 800 to 1,000. (: Smelting can be used to produce metallic tin or tin-lead alloy. Or, after washing with water, the precipitate is dissolved in a strong alkali. Strong bases include, but are not limited to: sodium hydroxide, potassium hydroxide, or mixtures thereof. Preferred bases are sodium hydroxide, potassium hydroxide, or a mixed solution thereof having an equivalent concentration between 20 and 70 N. The dissolution temperature used is between room temperature and 180 ° C, preferably between 80 and 160 t. The required time is more than i hours, preferably more than 5 hours, so that the tin content in the solution can reach more than 30 g / L, usually between 50 and 150 g / L. After dissolving the solids, this alkaline solution containing tin and lead is subjected to electrolytic reduction at 50 to 5C / litre to recover metal tin or tin alloy, and the potential difference between the anode and the anode is between I 5 to 70 volts is preferred. Metal tin or tin-lead alloys prepared by high temperature sintering method or electrolytic reduction method can be further electrolytically refined in stannous sulfate solution to obtain high purity Tin 'and its method are the same as those used to electrolytically refine crude copper to become refined copper. After the two-step oxidation at the same temperature, most of the tin ion and the wrong ion in the tin-lead waste liquid have been oxidized to form the tin and the wrong oxidation. Substances and hydroxides, and solid-liquid separation after the solid-liquid separation step, the crossing liquid contains only the ions and the wrong ions, and the copper ions of 2 to a few, the ions of a few to a few red or ferrous Ions and free nitric acid from 2.0 to 6.0 N. The filtration and liquid produced in the solid-liquid separation step are recovered in the recovery step. Neutralize it with sodium hydroxide or hydroxide and adjust its pH value to δ ~ ΐ3, so that the filter, liquid lock 200417626, and heavy metals such as steel, π, are formed by precipitation and precipitation of ions, Then, solid-liquid separation, 7 ~ A, "filter containing sodium nitrate or potassium nitrate and filter cake containing iron and copper oxides and gas oxide precipitates. The obtained filtrate can be used to treat hair after removing ammonia. The sodium nitrate or potassium nitrate crystals were obtained by crystallization method, and the filter cake was dissolved by adding a dilute sulfuric acid solution, and then copper sulfate and iron thiosulfate, or < ferrous iron ' Ferrous sulfate 'is either made of metal copper powder and ferrous sulfate by electrolytic reduction method, or made of copper and ferrous sulfate by electrolysis avoidance method. For the aforementioned extraction method, please refer to U.S. Patent Publication No. 4,252,621, Mainland China Patent Publication Nos. 1 154723A and 1297784A, etc., and use an organic extractant with the trade name [ιχ_54 to extract copper in a dilute sulfuric acid solution. The ions are then back-extracted with the concentrated sulfuric acid solution and dissolved in the reflux of the organic extractant ux-54, and then used to extract the copper ions in the dilute sulfuric acid bath. The copper sulfate solution is cooled, crystallized, or evaporated, filtered, and dried. Copper sulfate crystals were prepared by other steps, and the crystallization mother liquor produced by the filtration was also refluxed for re-extraction of copper ions in the organic extractant LIX-54; the aforementioned replacement method was to add iron powder to a dilute sulfuric acid solution to replace The copper ions in the solution are metallic copper powder, and the iron powder dissolves to form ferrous ions. 'The metal copper tin is produced by filtration and drying. The ferrous sulfate solution produced by the filtration is crystallized by evaporation to obtain ferrous sulfate, or Oxidation with oxygen, air, etc. to form a ferric sulfate solution; the aforementioned electrolytic reduction method is to place a dilute sulfuric acid solution in an electrolytic cell, and the solution is at a potential difference between cathode and anode of 5v The copper ions in it are reduced to metallic copper, and the residual ferrous sulfate solution is crystallized to obtain ferrous sulfate crystal II, or oxidized with oxygen, air, etc. to form a ferric sulfate solution. 15 200417626 [Example] Example 1: Take 5L of tin-lead stripping waste liquid, which contains about 10g / L Cu2 +, 30g / L Fe / Fe, 30g / L Sn2 + / Sn4 + And 10 ppm Pb2 +. After heating the waste liquid to 80 ° C, stirring and passing in oxygen for 2 hours, a large amount of tin oxide and hydroxide precipitates were formed in the waste liquid. Filtration and separation of tin oxides and hydroxides = sediments. At 8 ° C, the obtained solid tin oxide and chlorine oxide were combined in a 2L, 3N sodium hydroxide solution for 6 hours. Then, the temperature of the tin-containing alkali solution was raised to 95 ° C. After performing the high-temperature electrolytic reduction step under the condition that the potential difference between the anode and the anode was 3.0V, after 10 hours, the tin content in the solution was about 3 g / L, and about 12 leaves of tin were recovered. Example 2: Same as Example 1 Operation, after filtering and separating tin oxide and hydroxide deposits, 'wash and dry them, take the dry precipitate, add 2Og active slave and 80. 〇3g sodium carbonate, after mixing and grinding,实施 例 3: At 875 C high temperature for 4 hours, smelting to obtain 51.2g of metallic tin with a purity of 98.5%. Example 3:
2+ 取 4+1ΐΠ 内含約 5g/L cu2+、30g/L Fe2VFe3+、30g/L 。及1G ppm Pb離子之剝錫鉛廢液，將該廢液加熱 至9〇 C #拌亚通人氧氣2小時後，廢液中形成大量錫之 氧化物及氫氧化物沈殿物。在廢液溫度降低到赃以下時 ’過濾分離錫之氧化物及氯氧化物沈澱物。於100。。下，將 所付之固態锡之氣化物及* _ 虱化物及虱虱化物溶於300L·，濃度為3N的 200417626Take 2+ 4 + 1ΐΠ containing about 5g / L cu2 +, 30g / L Fe2VFe3 +, 30g / L. And 1G ppm Pb ion stripping tin and lead waste liquid. After heating the waste liquid to 90 ° C with Yatong human oxygen for 2 hours, a large amount of tin oxide and hydroxide Shen Dianwu were formed in the waste liquid. When the temperature of the waste liquid is lowered below the temperature, the oxide of tin and the oxide of chlorine oxide are separated by filtration. At 100. . Next, dissolve the solid tin vapors and * _ lice compounds and lice compounds in 300L · at a concentration of 3N 200417626
23kg金屬錫。 ，過濾去除溶液中尚未 sr溶液溫度至9 0 °c，於 高溫電解還原步驟歷時 令5g/L，並回收可得約 實施例4 ··23kg metal tin. ， The solution has been filtered to remove the temperature of the sr solution to 90 ° C. The temperature in the high-temperature electrolytic reduction step lasted 5 g / L and was recovered to obtain about Example 4 ··
於過濾分離錫之氧化物及氫氧化 沈澱物，加入63· 6g活性碳及 於950°C高溫下歷時4小 實施例5 : 編Ϊ虎 顏色 Cu(ppm) Fe(ppm) Sn(ppm) Pb(ppm) 1 淡綠 25. 84 22. 61 ND ND 2 淡綠 ND 14. 89 ND ND 3 淡黃 ND 3. 67 ND ND 實施例6 : 類似於實施1〜4的操作，於過濾分離錫之氧化物及氫 氧化物沈殺物後，沈澱物以溼法電解還原或以火法冶煉製 得金屬錫’濾液則以濃度約3N氫氧化鈉液中和並調整pH 至約11 ’渡液中形成褐色的鐵、銅、錫、鉛等氧化物及氫 氧化物的褐色濾餅與含硝酸鈉的淡綠色濾液，取3〇〇ml淡 綠色濾液，經蒸發結晶可製得約20g呈淡綠或淡黃的硝酸 鈉晶體，利用原子吸收光譜（A、A)分析其重金屬含量，結 果如下： _ __ 17 200417626 同實施例5，於過遽分離得含鐵、銅、錫 及氫氧化物的褐色濾餅後，將此褐色濾餅溶、 稀硫酸溶液t，形成微帶褐色的綠色溶液⑽的 差3· 0V及溫度15t的條件下電解2小時…二％極電位 乎穿+祜雷站、班広上 哈液中銅離子幾 子疋王破電解遇原成金屬銅，而使 人 為主的綠色溶f U為含硫酸亞鐵 〜以上實施例僅為本發明技術的示範例子，其並非用來 :疋，發明為特定形式，熟悉該項技術者在瞭解本發明之 ^，可依此進行任何修飾或改變，而該等修飾或改變應包八 於本案申請專利範圍之範疇内。 【圖式簡單說明】 (〜） 圖式部分 第〜圖為本發明之流程示意圖。The tin oxide and hydroxide precipitates were separated by filtration, and 63.6 g of activated carbon was added at a high temperature of 950 ° C for 4 minutes. Example 5: Weaving tiger color Cu (ppm) Fe (ppm) Sn (ppm) Pb (ppm) 1 Light green 25. 84 22. 61 ND ND 2 Light green ND 14. 89 ND ND 3 Light yellow ND 3. 67 ND ND After the oxides and hydroxides are killed, the precipitate is obtained by wet electrolytic reduction or smelting with fire. The filtrate is neutralized with a concentration of about 3N sodium hydroxide solution and the pH is adjusted to about 11%. Form a brown filter cake of brown iron, copper, tin, lead and other oxides and hydroxides with a pale green filtrate containing sodium nitrate. Take 300 ml of pale green filtrate and evaporate and crystallize to obtain about 20 g of pale green. Or light yellow sodium nitrate crystals, the content of heavy metals was analyzed by atomic absorption spectroscopy (A, A), and the results are as follows: _ __ 17 200417626 Same as in Example 5, the iron, copper, tin and hydroxide containing After the brown filter cake, the brown filter cake was dissolved and the dilute sulfuric acid solution t was formed to form a slightly brownish green solution. Electrolysis for 2 hours under the condition of 15t ... 2% of the electrode potential is almost worn through + Leizhan station, the copper ion in the Harbin solution. The king breaks the electrolysis into the original metal copper, and the human-based green solvent f U is Containing ferrous sulfate ~ The above examples are only exemplary examples of the technology of the present invention, and are not intended to: 疋, the invention is a specific form, those skilled in the art will understand the invention ^, and can make any modification or change accordingly, Such modifications or changes should be included in the scope of the patent application in this case. [Brief Description of the Drawings] (~) Schematic Drawings Figures ~ ~ are schematic diagrams of the process of the present invention.
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