201217542 六、發明說明： - 【發明所屬之技術領域】 以下揭露關於由無Pb廢焊料中回收貴重金屬，特定而言，一種 由無Pb廢焊料中回收錫或銀的方法，其中該無Pb廢焊料包含錫、 銀及其混合物。 【先前技術】 鑑於環境保護和資源循環，回收無Pb廢焊料中的錫和銀是重要 的。近來，由工業廢棄物（包括無Pb廢焊料）回收銀和錫一般可 分為電解法和簡單回收方法。 簡單回收方法是一種回收無Pb焊球源的方法，其中包括在高溫 下熔融無Pd廢焊料以初步自雜質中分離熔渣相，之後加入高純度 的錫於其中並調控錫的品質。然而，根據上述方法形成的焊球可 能需承擔品質惡化。 電解法為一種分離和回收的方法，其包含：製備一由高純度錫 (Sn)組成的陰極板，以及具有90至98重量％的無Pb焊料組成 的陽極板；在含有3至8體積％的H2SiF6、2至10體積％的H2S04 以及3體積％的Sn的電解液中進行電解；由陰極板回收Sn以及 由陽極細泥回收銀（Ag )，藉此回收高純度Sn。然而，上述方法 的缺點為產生大量有害廢水，其可能造成環境汙染且需要高初始 投資成本。 【發明内容】 為解決上述問題，本發明人研究處理廢焊料的技術，相較於相 201217542 關領域的已知方法，該技術更有效率且簡單，同時需要較低初始 成本。發明人發現在電解精煉過程使用含有氣離子（cr)的電解 液，可主要解決增加Sn或Ag回收率的問題，藉此完成本發明。 因此，本發明的一目的為提供一種由無Pb廢焊料回收貴重金屬的 方法，其優勢在於可克服現有由廢焊料中經萃取、分離和/或精煉 貴重金屬方法的困難及/或重複性；以及，可有效且經濟地回收高 純度的Sn或Ag。 本發明的一實施例係提供一種由無P b廢焊料中回收貴重金屬的 方法，更特定而言，一種由包含Sn、Ag或其混合物的無Pb廢焊 料中回收Sn或Ag的方法。 在一般方面，一種由無Pb廢焊料中回收Sn或Ag的方法，其包 含：（1)由無Pb廢焊料製備一陽極，其中該無Pb廢焊料包含 Sn、Ag或其混合物；（2)施加電流至含有氯離子（Cl_)之電解 液中之操作（1)所製備的陽極以及一陰極；（3)透過施加電流 所起始的反應，濃縮Ag於形成在該陽極上之陽極細泥中，同時電 沉積Sn於該陰極上；以及（4)回收電沉積的Sn或自該陽極細泥 回收濃縮的Ag。 於另一般方面，一種由無Pb廢焊料中回收Sn或Ag的方法，其 包含：（1)由無Pb廢焊料製備一陽極，其中該無Pb廢焊料包含 Sn、Ag或其混合物；（2)施加電流至含有氯離子（Cl—)之電解 液中之所製備的陽極以及一陰極；（3)透過施加電流所起始的反 應，濃縮Ag作為一含於該陽極上之陽極細泥中的材料，同時電沉 積Sn於該陰極上；以及（4)回收含有Ag濃縮於其中的陽極細泥， 201217542 以化學方法溶解該、σ 分離後回㈣並進行其固液分離；（5)使用固液 ^ ^ . 藉由，儿澱與由濾液所產生的Ag化合物的還 原作用而獲得的Ag，以形士、』 行Ag的電解精煉；以及^ 極，並在喊銀電解液中進 作⑸之電沉積的々。回收操作（3)之電沉積的"或操 根據本發明由無Pb麻悝粗占 氣離子⑴_)的電2 收如或々的方法’可使用含有 本七明由無Pb廢焊料中回收Sn或Ag的方法可包 含施加電流至含有- 使用包人Sn、Α ，解液中之陽極和陰極，該陽極和陰極係 二_ g或其混合物的無Pb廢焊料而形成，以防止Sn 雷儿灰’同時增進陽極細泥中銀的富集率（enrkhmemme) 和Sn電沉積的電流效率。 在另一般方面，— 廢焊料中回收^的方法包含：進 離二泥，並進行固液分離™液分 合物的還原作用而^的8；及藉由沉澱與由據液所生產的^化 電解液中崎A㈣§叫絲Α§陽極，然後在確酸銀 "電解精煉’從而可回收高純度和高產量的〜。 以下將更詳述本發明。 含本=可提供-種由無Pb廢焊料中回收S4Ag的方法，其包 %、b廢焊料製備—陽極，其中該無朴廢焊料包含 ^ . 2 '、此合物；（2)施加電流至含有氯離子（cr)之電解 液中之所製備的陽極以及一陰極;(3)透過施加電流： 201217542 應，濃縮Ag作為一含於該陽極上之陽極細泥中的材料，同時電沉 積Sn於該陰極上；以及（4 )回收電沉積的Sn或自該陽極細泥回 收濃縮的Ag。 根據本發明，該由無Pb廢焊料中回收Sn或Ag的方法可進一步 包含：在操作（3)之後，回收含有Ag濃縮於其中的陽極細泥並 相繼進行其化學方式溶解及固液分離；以及使用固液分離後而獲 得的未溶解的Ag殘餘物，以及透過沉澱與還原作用由存在於回收 的濾液中之溶解的Ag而獲得的Ag，以形成粗Ag陽極，並在硝酸 銀電解液中進行Ag的電解精煉。 更特定而言，本發明可提供一種由無Pb廢焊料中回收Sn或Ag 的方法，其包含：（1)由無Pb廢焊料製備一工作電極（即一陽 極），其中該無Pb廢焊料包含Sn、Ag或其混合物；（2)施加電 流至含有氣離子（cr)之電解液中之操作（1)所製備的陽極以 及一陰極；（3)透過施加電流所起始的反應，濃縮Ag作為一含 於該陽極上之陽極細泥中的材料，同時電沉積Sn於該陰極上；以 及（4)進行以化學方式溶解與固液分離該含有Ag濃縮於其中的 陽極細泥；（5)使用固液分離後回收作為殘餘物的Ag以及藉由 沉澱與還原作用由濾液所獲得的Ag，以形成粗Ag陽極，並在硝 酸銀電解液中進行Ag的電解精煉；以及（6)回收操作（3)之電 沉積的Sn或操作（5 )之電沉積的Ag (參見第1圖）。 根據本發明，操作（1)可包含在400°C溫度下熔化並洗鑄該無 Pb廢焊料，以製備用於初步電解精煉之陽極。無Pb廢焊料並無 特別限制，只要其含有Sn以及Ag。 201217542 根據本發明，初步電解精煉的 目的是為了由陰極自收高純度201217542 VI. Description of the Invention: - Technical Field of the Invention The following discloses a method for recovering precious metals from Pb-free waste solder, in particular, a method for recovering tin or silver from Pb-free waste solder, wherein the Pb-free waste The solder contains tin, silver, and mixtures thereof. [Prior Art] In view of environmental protection and resource recycling, it is important to recover tin and silver in Pb-free solder. Recently, the recovery of silver and tin from industrial waste (including Pb-free waste solder) is generally classified into an electrolysis method and a simple recovery method. The simple recovery method is a method of recovering a Pb-free solder ball source, which comprises melting a Pd-free solder at a high temperature to initially separate the slag phase from the impurities, and then adding high-purity tin therein and regulating the quality of the tin. However, the solder balls formed according to the above method may be subject to deterioration in quality. The electrolysis method is a separation and recovery method comprising: preparing a cathode plate composed of high-purity tin (Sn), and an anode plate having a composition of 90 to 98% by weight of Pb-free solder; containing 3 to 8 vol% Electrolysis was carried out in an electrolyte of H2SiF6, 2 to 10% by volume of H2S04, and 3 vol% of Sn; and Sn was recovered from the cathode plate and silver (Ag) was recovered from the anode fine mud, thereby recovering high-purity Sn. However, the above method has the disadvantage of producing a large amount of harmful waste water, which may cause environmental pollution and requires high initial investment cost. SUMMARY OF THE INVENTION In order to solve the above problems, the inventors have studied a technique for treating waste solder, which is more efficient and simpler than a known method in the field of 201217542, and requires a lower initial cost. The inventors have found that the use of an electrolytic solution containing a gas ion (cr) in an electrolytic refining process can mainly solve the problem of increasing the recovery rate of Sn or Ag, thereby completing the present invention. Accordingly, it is an object of the present invention to provide a method for recovering precious metals from Pb-free waste solder which has the advantage of overcoming the difficulties and/or reproducibility of existing methods for extracting, separating and/or refining precious metals from spent solder; And, high purity Sn or Ag can be efficiently and economically recovered. An embodiment of the present invention provides a method of recovering precious metals from Pb-free waste solder, and more particularly, a method of recovering Sn or Ag from a Pb-free waste solder containing Sn, Ag or a mixture thereof. In a general aspect, a method for recovering Sn or Ag from a Pb-free waste solder, comprising: (1) preparing an anode from a Pb-free waste solder, wherein the Pb-free waste solder comprises Sn, Ag, or a mixture thereof; (2) An anode and a cathode prepared by the operation (1) in which an electric current is applied to an electrolyte containing chloride ions (Cl_); (3) a reaction initiated by applying an electric current, and Ag is concentrated on an anode slime formed on the anode And simultaneously depositing Sn on the cathode; and (4) recovering the electrodeposited Sn or recovering the concentrated Ag from the anode slime. In another general aspect, a method of recovering Sn or Ag from a Pb-free waste solder, comprising: (1) preparing an anode from a Pb-free waste solder, wherein the Pb-free waste solder comprises Sn, Ag, or a mixture thereof; Applying an electric current to the prepared anode and a cathode in an electrolyte containing chloride ions (Cl-); (3) reacting by applying an electric current to concentrate Ag as an anode slime contained in the anode Material, while electrodepositing Sn on the cathode; and (4) recovering the anode fine mud containing Ag concentrated therein, 201217542 chemically dissolving the σ separation and back (4) and performing solid-liquid separation; (5) use Solid-liquid ^ ^ . By means of the reduction of the Ag and the Ag compound produced by the filtrate, the Ag is obtained by electrolysis refining of Ag, and the electrode, and is made in the silver electrolyte. (5) Electrodeposited ruthenium. The method of "electrodeposition of the recovery operation (3)" or the method of "receiving or enthalpy of electricity by the Pb-free paralysis-free gas ion (1)_) according to the present invention can be recovered from the non-Pb waste solder containing the present invention. The method of Sn or Ag may comprise applying an electric current to a Pb-free solder containing - using an anode and a cathode in a smear, a ruthenium solution, a cathode and a cathode system, or a mixture thereof, to prevent Sn The ash is also used to increase the enrichment rate of silver in the anode fine mud (enrkhmemme) and the current efficiency of Sn electrodeposition. In another general aspect, the method for recovering from the waste solder comprises: removing the two muds, and performing the reduction of the solid-liquid separation solution of the TM liquid; and the precipitation by the liquid and the liquid produced by the liquid The electrolyte is in the form of a high-purity and high-yield ~. The invention will be described in more detail below. Included = can provide - a method for recovering S4Ag from Pb-free waste solder, the package %, b waste solder preparation - anode, wherein the no-waste solder contains ^ 2 ', the compound; (2) the application of current The prepared anode and the cathode in the electrolyte containing chloride ion (cr); (3) the applied current: 201217542, Ag should be concentrated as a material contained in the anode fine mud on the anode, and electrodeposited Sn is on the cathode; and (4) recovering the electrodeposited Sn or recovering the concentrated Ag from the anode slime. According to the present invention, the method for recovering Sn or Ag from the Pb-free waste solder may further include: after the operation (3), recovering the anode fine mud containing the Ag concentrated therein and sequentially performing its chemical dissolution and solid-liquid separation; And an undissolved Ag residue obtained after solid-liquid separation, and Ag obtained by dissolving Ag dissolved in the recovered filtrate by precipitation and reduction to form a crude Ag anode, and in a silver nitrate electrolyte Electrolytic refining of Ag is performed. More specifically, the present invention can provide a method for recovering Sn or Ag from a Pb-free waste solder, comprising: (1) preparing a working electrode (ie, an anode) from a Pb-free waste solder, wherein the Pb-free waste solder Containing Sn, Ag or a mixture thereof; (2) an anode prepared by the operation (1) and a cathode applied by applying an electric current to an electrolyte containing gas ions (cr); (3) a reaction initiated by applying an electric current, concentrating Ag as a material contained in the anode fine mud on the anode, while simultaneously depositing Sn on the cathode; and (4) performing chemical dissolution and solid-liquid separation of the anode fine mud containing Ag concentrated therein; 5) recovering Ag as a residue and Ag obtained from the filtrate by precipitation and reduction using solid-liquid separation to form a crude Ag anode, and performing electrolytic refining of Ag in a silver nitrate electrolyte; and (6) recycling Electrodeposited Sn of operation (3) or electrodeposited Ag of operation (5) (see Fig. 1). According to the present invention, the operation (1) may comprise melting and washing the Pb-free waste solder at a temperature of 400 ° C to prepare an anode for preliminary electrolytic refining. The Pb-free solder is not particularly limited as long as it contains Sn and Ag. According to the present invention, the purpose of preliminary electrolytic refining is to self-receive high purity from the cathode.
本發明具重大的意義。 根據本發明，所添加cr的濃度可在〇 05至〇 5莫耳/公升的範 圍’較佳0.1至0.3莫耳/公升。若C1—濃度低於0_〇5莫耳/公升， Ag濃度的增進以及防止產生Sn氧化物沉澱的效果可能會下降。 另一方面，即使在cr濃度高於0.5莫耳/公升’ Ag的富集率與其 在C1—濃度為0.5莫耳/公升時並無顯著差異’並且進一步需承擔 電解液腐蝕電位增加的問題。 添加cr至電解液可使用含有cr的酸或鹽類的任何一者執行， 較佳使用選自HC1、NaCl、KC1及ΝΗβΙ之至少—者，更佳使用 因陽離子之低汙染的HC1。 使用作為電解液的硫酸溶液可具有0.5至2莫耳/公升的硫酸濃 度。若硫酸濃度超出上述範圍，電解液之離子導電度可能會降低， 反而會增加過量電壓。此外，過量電壓可能因陽極細泥的生成而 更顯著。因此，過程維持時間（即保持時間）可能會大幅下降， 因此，將不能達成本發明目的。 根據本發明，電解液的溫度可為25至60°C，係考量要維持—值 定溫度消耗太多能源所導致的經濟損失而嚴格界定此溫度範圍。 201217542 根據本發明，電解可在5至25毫安培/平方公分的電流密度條件 下。 在操作（3)之後，含有Ag的陽極細泥層係形成於該陽極表面 上，電壓因而增加。當電壓增加越高時，保持時間越短。此外， 電壓的增加速率會在硫酸濃度增加以及電流密度增加的情況下迅 速地增加。因此，為適當增加電壓以及電解速率，電流密度較佳 為10毫安培/平方公分（參見第3圖）。 根據本發明，在操作（3)之後執行的操作（4)及（5)是為了 由濃縮有Ag的陽極細泥中得到純度的Ag粉末。更特定而言^ 該濃縮有Ag的陽極細泥相繼進行化學方式溶解及固化分離。然 後，初步回收固液分離後保留作為殘餘物的Ag，同時透過沉澱與 還原作用回收部份溶解且含於濾液中的Ag部份作為Ag粉末。上 述二Ag部分可經熔解、澆鑄或鑄造以及燒結以形成粗Ag陽極。 最後，在硕酸銀電解液中執行Ag的電解精煉，以完成上述操作。 根據本發明，在操作（3)之後，使用該濃縮有Ag的陽極細泥 所形成的粗Ag陽極，實質上可使用Ag殘餘物與Ag粉末製造， 該Ag殘餘物係藉由以化學方式溶解濃縮有Ag的陽極細泥並進行 其固液分離而獲得，該A g粉末係藉由化學沉澱與還原該固液分離 後所回收的渡液所產生。 固液分離可實質上包含於溶解濃縮有Ag的陽極細泥於氫氣 酸、墙酸或王水中之後，固液分離該溶解產物。化學沉澱係藉由 添加離子，如氯離子（Cl—)、硫酸根離子（S042—)、磷酸根離子 (P043—)或其類似物至該固液分離後所回收的濾液中，以產生 201217542The invention is of great significance. According to the present invention, the concentration of added cr may be in the range of 〇 05 to 〇 5 mol/liter, preferably 0.1 to 0.3 mol/liter. If the concentration of C1 - is less than 0 〇 5 m / liter, the increase in Ag concentration and the effect of preventing the precipitation of Sn oxide may be lowered. On the other hand, even when the Cr concentration is higher than 0.5 mol/liter AH, the enrichment ratio is not significantly different from that at C1 - concentration of 0.5 mol/liter, and further, there is a problem that the electrolyte corrosion potential is increased. The addition of cr to the electrolytic solution may be carried out using any one of an acid or a salt containing Cr, preferably at least one selected from the group consisting of HCl, NaCl, KC1 and ΝΗβΙ, and it is more preferable to use HC1 which is low in contamination by cations. The sulfuric acid solution used as the electrolyte may have a sulfuric acid concentration of 0.5 to 2 mol/liter. If the sulfuric acid concentration is outside the above range, the ionic conductivity of the electrolyte may be lowered, and the excess voltage may be increased. In addition, excessive voltage may be more pronounced due to the formation of anode fines. Therefore, the process maintenance time (i.e., hold time) may be drastically lowered, and therefore, the object of the present invention will not be attained. According to the present invention, the temperature of the electrolyte may be from 25 to 60 ° C, which is strictly defined by the economic loss caused by the consumption of too much energy by the temperature. 201217542 According to the present invention, electrolysis can be carried out at a current density of 5 to 25 mA/cm 2 . After the operation (3), an anode fine mud layer containing Ag is formed on the surface of the anode, and the voltage is thereby increased. When the voltage increase is higher, the hold time is shorter. In addition, the rate of increase in voltage rapidly increases as the concentration of sulfuric acid increases and the current density increases. Therefore, in order to appropriately increase the voltage and the electrolysis rate, the current density is preferably 10 mA/cm 2 (see Fig. 3). According to the present invention, the operations (4) and (5) performed after the operation (3) are for obtaining Ag powder of a purity from the anode fine mud in which Ag is concentrated. More specifically, the anode fine sludge concentrated with Ag is successively subjected to chemical dissolution and solidification separation. Then, the Ag as a residue is retained after the preliminary recovery of the solid-liquid separation, and the Ag portion partially dissolved and contained in the filtrate is recovered as an Ag powder by precipitation and reduction. The above two Ag moieties may be melted, cast or cast and sintered to form a coarse Ag anode. Finally, electrolytic refining of Ag is performed in a silver silicate electrolyte to complete the above operation. According to the present invention, after the operation (3), the crude Ag anode formed using the Ag-concentrated anode fine mud can be substantially produced by using Ag residue and Ag powder, which is chemically dissolved. It is obtained by concentrating an anode fine sludge of Ag and performing solid-liquid separation thereof, which is produced by chemical precipitation and reduction of the liquid recovered after the solid-liquid separation. The solid-liquid separation may be substantially included in the solid solution to dissolve the dissolved product after dissolving the anode fine mud concentrated with Ag in hydrogen acid, wall acid or aqua regia. The chemical precipitation is carried out by adding ions such as chloride ion (Cl-), sulfate ion (S042-), phosphate ion (P043-) or the like to the filtrate recovered after the solid-liquid separation to produce 201217542
Ag沆澱物 更特定而言，此由電沉積的Sn或濃縮有Ag的陽極細苑中 Sn或Ag可藉由以下方式進行.在陰極上之電沉積的Sn 以超純水（通常稱去離子水（DI水））清洗該陰極’並乾 回收 的情况， ‘燥獲得針 狀粉末形式的產物；以及，在濃縮於陽極細泥中的Ag的情％ 過後處理回收該陽極細泥並由回收的陽極細泥中分離Ag。 透 此後處理可包含：在預定的間隔時間取出形成於該陽極表面 的陽極細泥層；將所收集的陽極細泥層以5°/❶氫氣酸溶液和n 叫水 清洗並過濾該清洗的產物以回收該陽極細泥；化學方式溶解陽極 細泥於濃氫氣酸或硝酸及/或王水以獲得Ag殘餘物，並進—步進 行固液分離β由所回收的濾液獲得Ag沉澱物。將上述獲得的Ag 殘餘物及Ag沉澱物過濾並以DI水清洗以得到最終產物。 根據本發明，可藉由添加會與Ag反應並形成沉澱的離子，如氯 離子（cr)、硫酸根離子（s〇42_)、磷酸根離子（p〇43-)或其類 似物至該濾液中，以形成Ag沉澱物，藉此產生如AgCl、AgS04、 Ag3P04或其類似物的Ag沉澱物。在此方面，可藉化學還原作用 由該Ag沉澱物回收Ag粉末，如以下反應流程所示： [反應流程] 2AgCl + Na2C03 今 2NaCl + C02 + 1/202 + Ag 2AgCl + 2NaOH -> Ag20 + 2NaCl + H20 Ag20 + HCOOH + 2Ag + C02 + H20 根據以上化學反應回收的Ag粉末及Ag殘餘物可合併並熔化 201217542 (或燒結），接著澆鑄以形成用於Ag電解精煉的粗Ag陽極。可 在970°C或更高的溫度下執行熔化，而可在700°C或更高的溫度下 執行燒結。此外，使用所形成的粗Ag陽極，藉由在含有硝酸的硝 酸銀溶液（AgN03)中的二次電解精煉，可獲得純度99.99%或更 高的Ag。 其他特點及態樣將透過下文詳細敘述、圖式以及請求項而更加 清楚。 【實施方式】 將參照以下實施例詳細描述本發明，然而，這些實施例僅提供 用於例示本發明，本發明範圍並非特別受限於此。 除文中另有界定外，本說明書所用之技術和/或科學術語之意義 為本發明所屬領域具有通常知識者所通常理解者。下文說明和所 附圖式中，此領域已知的技術配置和/或功能的詳細敘述為簡潔之 目的將予以省略，而不會模糊本發明之精隨。 [比較例] 一無Pb廢焊料樣品包含以下主要貴重金屬成分，即93%的Sn、 4%的Ag以及0.9%的Cu，其於400°C熔化並澆鑄形成一陽極。所形 成的陽極經加工以具有4平方公分的暴露面積。將260毫升具有1莫 耳/公升濃度的硫酸電解液置於一電解浴中，該電解浴配有與水浴 相連的水套以控制溫度，以及使用一具有25平方公分暴露面積的 鉑板作為陰極。在10毫安培/平方公分的電流密度及40°C溫度的條 件下，進行25小時的電解精煉。 201217542 [實施例1] _ -無Pb廢焊料樣品包含以下主要責重金屬成分即抓的％、 4。/。的Ag以及〇·9%的Cu，其於彻。c炫化並洗鑄形成一陽極。所形 成的陽極經加工以具有4平方公分的暴露面積。將毫升具有4 耳/么升i度並含有濃度為(^莫耳/公升的氫氣酸的硫酸電解液置 於-電解財，該電解浴配有與水浴相連的水套以㈣溫度，以 及使用-具有25平方公分暴露面積的鈾板料陰極。在毫安培/ 平方公分的電流密度及4〇°C溫度的條件下，進行25小時的電解精 煉。 [實施例2] -無Pb廢焊料樣品包含以下主要貴重金屬成分，即93%的如、 4%的Ag以及0.9%的Cu，其於400。(：熔化並澆鑄形成一陽極。所形 成的陽極經加工以具有4平方公分的暴露面積。將26〇毫升具有1莫 耳/公升/辰度並含有濃度為0.2莫耳/公升的氫氣酸的硫酸電解液置 於一電解浴中，該電解浴配有與水浴相連的水套以控制溫度，以 及使用一具有25平方公分暴露面積的鉑板作為陰極。在1〇毫安培/ 平方公分的電流密度和40°C溫度的條件下，進行25小時的電解精 煉。 [實施例3] 一無Pb廢焊料樣品包含以下主要貴重金屬成分，即93%的Sn、 4%的Ag以及〇·9%的Cu ’其於4〇〇t熔化並澆鑄形成一陽極。所形 成的陽極經加工以具有4平方公分的暴露面積。將260毫升具有1莫 12 201217542 耳/公升濃度並含有濃度為〇 3莫耳/公升的氫氯酸的硫酸電解液置 於電解浴中，該電解浴配有與水浴相連的水套以控制溫度，以 及使用一具有25平方公分暴露面積的鉑板作為陰極。在1〇毫安培/ 平方公分的電流密度和4〇充溫度的條件下，進行25小時的電解精 煉。 [實施例4] 一無Pb廢焊料樣品包含以下主要貴重金屬成分，即93%的^、 4%的Ag以及〇.9〇/〇的Cu，其於400〇c熔化並澆鑄形成一陽極。所形 成的陽極經加工以具有56平方公分的暴露面積。將4〇〇〇毫升具有1 莫耳/公升濃度並含有濃度為〇 2莫耳/公升的氫氣酸的硫酸電解液 置於一電解冷中，該電解浴配有與水浴相連的水套以控制溫度， 以及使用一具有255平方公分暴露面積的經sn塗覆之鈦板作為陰 極。在10毫安培/平方公分的電流密度和40〇c溫度的條件下，進行 25小時的電解精煉。 [實施例5] 將0.2〇33公克上述實施例4所製備濃縮有Ag的陽極軟泥，置於4〇 毫升35%的氫氣酸中，在沸點溫度下溶解3〇分鐘，過濾並清洗， 獲得0.〇428公克溶解的Ag殘餘物。 [實施例6] 實施例5所獲得的Ag溶解殘餘物粉末（Ag 99.5% )以及AgCl沉殿 物以及另外由氫氧化鈉（NaOH)與甲酸（HCOOH)反應所形成 的Ag粉末混合在一起，並形成一直徑5〇毫米的盤形，接著在75〇 13 201217542 °C溫度下燒結1小時，以形成用於Ag電解精煉的粗Ag陽極。 調整該由Ag製成的粗Ag陽極的暴露面積為9平方公分。使用容 量500毫升的聚四氟乙烯（PTFE)電解浴進行電解精煉。將該由 Ag製成之粗Ag陽極置入由聚丙烯（PP)製成且具有500網格的濾 布，以防止電解液污染。 用於電解精煉由Ag製成的粗Ag陽極的陰極是使用純度99.9%或 更高的鈦材料製成，並具有9平方公分的暴露面積。此處所使用的 電解液為含有0.5莫耳/公升AgN03並具有0.5莫耳/公升濃度的 hno3溶液。 在30毫安培/平方公分電流密度的條件下，進行2小時電解精煉。 結果證實Ag電沉積量為2.172公克以及電流效率為99.9%或更高。 分析電解精煉下Ag成份的結果發現，Ag的純度為99.99%或更高。 [實驗實施例1] 關於比較例以及實施例1至3中的電解精煉，確認電化學溶解/純 化程序與硫酸電解液中cr濃度的關係。 [表1] 氫氣酸濃度 陽極溶解量 (公克） 電沉積 (公克） 陽極軟泥 (公克） 電流效率 比較例 - 2.3987 1.8772 0.1818 84.7 實施例1 0.1 2.4048 1.8733 0.1872 84.5 實施例2 0.2 2.4022 1.9630 0.1837 88.6 實施例3 0.3 2.4017 2.0449 0.1792 92.2 如表1所示，在比較例的情況中，陽極溶解量為2.3987公克， 鉑陰極板上的Sn電沉積量為1.8772公克，以及陽極細泥的生成量 14 201217542 為0.1818公克。該電沉積Sn呈現一針狀且具有99.9%或更高的純 度。陽極細泥中的Ag含量為43.1%而陽極細泥中的Ag富集率為 81.7%。於此，就Sn2+電沉積而言，計算出電流效率為84.7%，且 經放置一段時間，由電解液生成白色Sn氧化物沉殿物。 在實施例1的情況中，陽極溶解量為2.4048公克，鉑陰極板上 的Sn電沉積量為1.8733公克，以及陽極細泥的生成量為0.1872 公克。該電沉積Sn呈現一針狀且具有99.9%或更高的純度。陽極 細泥中的Ag含量為46.23%而陽極細泥中的Ag富集率為89.9%。 於此，就Sn2+電沉積而言，計算出電流效率為84.5%，並且即使 經放置一段時間，電解液中也不會發生Sn氧化物的沉澱。 在實施例2的情況中，陽極溶解量為2.4022公克，鉑陰極板上 的Sn電沉積量為1.9630公克，以及陽極細泥的生成量為0.1837 公克。該電沉積Sn呈現一針狀且具有99.9%或更高的純度。陽極 細泥中的Ag含量為48.6%而陽極細泥中的Ag富集率為92.9%。 於此，就Sn2+電沉積而言，計算出電流效率為88.6%，並且即使 經放置一段時間，電解液中也不會發生Sn氧化物的沉澱。 在實施例3的情況中，陽極溶解量為2.4017公克，鉑陰極板上 的Sn電沉積量為2.0449公克，以及陽極細泥的生成量為0.1792 公克。該電沉積Sn呈現一針狀且具有99.9%或更高的純度。陽極 細泥中的Ag含量為50.5%而陽極細泥中的Ag富集率為94.2%。 於此，就Sn2+電沉積而言，計算出電流效率為92.2%，並且即使 經放置一段時間，電解液中也不會發生Sn氧化物的沉澱。 由上述實施例1至3以及第2圖結果可看出，藉由添加C1+至電 15 201217542 解液中，可預防電解液中Sn氧化物的沉澱，且陽極細泥中的Ag 富集率提升。 實施例1至3的結果證實，可克服現有由廢焊料中萃取、分離 以及純化貴重金屬方法的困難及/或重複性，並且可有效且經濟地 回收Sn或Ag。 [實驗實施例2] 在實施例3中溫度和電解液組成的條件下，分析電化學溶解/純 化程序的結果與電流密度的關係。 [表2] 成为 含量（％) 10毫安培/平方公分 25毫安培/平方公分 50毫安培/平方公分 Ag 50.54 48.17 55.64 Sn 34.67 37.27 31.70 Cu 11.50 11.31 6.64 0 3.2 3.24 5.96 s 0.09 - 0.06 Cl - - - 上述表2和第3圖的結果證實陽極細泥的組成變化與電流密度 增加之間的關係。此外，也可看出電壓隨著形成於陽極上之細泥 層的增加而提高。再者，已發現可藉由將電壓的增加作最大限度 的延緩得以延長過程維持時間（即保有時間）時的較佳電流密度 為10毫安培/平方公分。 [實驗實施例3] 分析實施例4和5中所獲得的陽極細泥的組成以及固液分離後 由該陽極細泥所獲得的Ag殘餘物的組成。 201217542 如第4圖所示，電沉積Sn呈現一針狀且具有99.9%或更高的純 度。陽極細泥中的Ag含量為47.4%且Ag富集率為95%。 此外，如第5圖所示，陽極細泥的溶解Ag殘餘物的純度為 99.5%。將濾液與0.5莫耳/公升的NaCl溶液反應得到0.0702公克 的AgCl沉澱物，具有75.3%的Ag含量。由於Ag的總量為0.0957 公克，故可回收99.5%的Ag。 正如上所述，本發明由無Pb廢焊料中回收Sn或Ag的方法可克 服由現有廢焊料中萃取、分離以及純化貴重金屬方法的困難及重 複性，並且可有效且經濟地回收高純度的Sn或Ag。 根據本發明由無Pb廢焊料中回收Sn或Ag的方法，其係在電解 精煉中使用含有氣離子（Cl_)的電解液，用以防止Sn氧化物沉 澱，此為相關技術中增進Sn或Ag的回收率的一個問題。此外， 由於提高了陽極細泥中的Ag富集率以及Sn電沉積率，因而提高 Sn或Ag的回收率。 【圖式簡單說明】 第1圖為顯示根據本發明之一具體實施態樣由無Pb廢焊料中回 收Sn或Ag的方法的示意圖； 第2圖例示根據本發明之一具體實施態樣電化學溶解/純化程序 與硫酸電解液中cr濃度關係的結果； 第3圖例示根據本發明實施例3之電解液的預定溫度與組成的 條件下，電化學溶解/純化程序與電流密度關係的結果； 第4圖例示本發明實施例4所獲得的陽極細泥的組成的分析結 17 201217542 果；以犮 第5圖例示本發明實施例5所獲得的Ag殘餘物的組成的分析結 果。 【主要元件符號說明】 (無） 18More specifically, the Ag yttrium deposit may be carried out by electrodepositing Sn or Ag-concentrated anode enamel in the following manner. The electrodeposited Sn on the cathode is ultrapure water (usually called Ionic water (DI water)) cleaning the cathode 'and dry recovery, 'drying to obtain a product in the form of a needle powder; and, after the concentration of Ag concentrated in the anode slime, the anode fine mud is recovered and treated by Ag is separated from the recovered anode fine mud. The post-treatment may include: taking out an anode fine mud layer formed on the surface of the anode at a predetermined interval; washing the collected anode fine mud layer with a 5°/❶ hydrogen acid solution and n water and filtering the washed product The anode fine mud is recovered; the anode fine mud is chemically dissolved in concentrated hydrogen acid or nitric acid and/or aqua regia to obtain Ag residue, and the solid-liquid separation is further carried out. β The Ag precipitate is obtained from the recovered filtrate. The Ag residue obtained above and the Ag precipitate were filtered and washed with DI water to give a final product. According to the present invention, an ion which reacts with Ag and forms a precipitate, such as chloride ion (cr), sulfate ion (s〇42_), phosphate ion (p〇43-) or the like, can be added to the filtrate. In order to form an Ag precipitate, thereby producing an Ag precipitate such as AgCl, AgS04, Ag3P04 or the like. In this respect, the Ag powder can be recovered from the Ag precipitate by chemical reduction, as shown in the following reaction scheme: [Reaction scheme] 2AgCl + Na2C03 Present 2NaCl + C02 + 1/202 + Ag 2AgCl + 2NaOH -> Ag20 + 2NaCl + H20 Ag20 + HCOOH + 2Ag + C02 + H20 Ag powder and Ag residue recovered according to the above chemical reaction may be combined and melted 201217542 (or sintered), followed by casting to form a coarse Ag anode for Ag electrolytic refining. The melting can be performed at a temperature of 970 ° C or higher, and the sintering can be performed at a temperature of 700 ° C or higher. Further, using the formed crude Ag anode, Ag can be obtained with a purity of 99.99% or more by secondary electrolytic refining in a nitric acid-containing silver nitrate solution (AgN03). Other features and aspects will become apparent through the detailed description, drawings and claims below. [Embodiment] The present invention will be described in detail with reference to the accompanying Examples, however, these Examples are only provided to illustrate the invention, and the scope of the invention is not particularly limited thereto. Unless otherwise defined herein, the meaning of the technical and/or scientific terms used in the specification is to be understood by those of ordinary skill in the art. Detailed descriptions of the technical configurations and/or functions that are known in the art are omitted for the sake of brevity in the following description and the accompanying drawings, without obscuring the invention. [Comparative Example] A Pb-free waste solder sample contained the following main precious metal components, namely, 93% of Sn, 4% of Ag, and 0.9% of Cu, which were melted at 400 ° C and cast to form an anode. The resulting anode was processed to have an exposed area of 4 square centimeters. 260 ml of a sulfuric acid electrolyte having a concentration of 1 mol/liter was placed in an electrolytic bath equipped with a water jacket connected to a water bath to control the temperature, and a platinum plate having an exposed area of 25 cm 2 was used as a cathode. . Electrolytic refining was carried out for 25 hours under a current density of 10 mA/cm 2 and a temperature of 40 °C. 201217542 [Example 1] _ - The Pb-free waste solder sample contained the following main components of the metal component, namely, scratched %, 4. /. Ag and 〇·9% of Cu, which is in the root. c simplifies and washes to form an anode. The resulting anode was processed to have an exposed area of 4 square centimeters. The milliliters have a sulfuric acid electrolyte having a concentration of 4 ohms per liter and containing a hydrogen gas at a concentration of (^ mol/liter of hydrogen gas, the electrolytic bath is provided with a water jacket connected to the water bath at (iv) temperature, and used - Uranium sheet cathode with an exposed area of 25 square centimeters. Electrolytic refining was carried out for 25 hours at a current density of mA/cm 2 and a temperature of 4 ° C. [Example 2] - No Pb waste solder sample Contains the following major precious metal components, namely 93%, 4% Ag and 0.9% Cu, at 400. (: Melted and cast to form an anode. The resulting anode is machined to have an exposed area of 4 square centimeters 26 cc of sulfuric acid electrolyte having 1 mol/liter/min and containing hydrogen gas at a concentration of 0.2 mol/liter is placed in an electrolytic bath equipped with a water jacket connected to the water bath to control The temperature, and a platinum plate having an exposed area of 25 cm 2 was used as a cathode. Electrolytic refining was carried out for 25 hours under a current density of 1 Torr mA / cm 2 and a temperature of 40 ° C. [Example 3] Pb-free solder samples contain the following main The precious metal components, namely 93% Sn, 4% Ag, and 9% 9% Cu's were melted and cast at 4 Torr to form an anode. The resulting anode was processed to have an exposed area of 4 square centimeters. A 260 ml sulfuric acid electrolyte having a concentration of 1 at 12 201217542 ears/liter and containing hydrochloric acid at a concentration of 〇3 mol/liter is placed in an electrolytic bath equipped with a water jacket connected to the water bath to control the temperature. And using a platinum plate having an exposed area of 25 square centimeters as a cathode. Electrolytic refining was carried out for 25 hours under a current density of 1 Torr ampere/cm 2 and a temperature of 4 Torr. [Example 4] The Pb waste solder sample contains the following main precious metal components, namely 93% of ^, 4% of Ag and 〇.9〇/〇 of Cu, which is melted and cast at 400 ° C to form an anode. The formed anode is processed to Has an exposed area of 56 square centimeters. 4 cc of sulfuric acid electrolyte having a concentration of 1 mol/liter and containing hydrogen peroxide at a concentration of 〇2 mol/liter is placed in an electrolytic cold bath equipped with a water jacket connected to the water bath to control the temperature to And using a Sn-coated titanium plate having an exposed area of 255 square centimeters as a cathode. Electrolytic refining was carried out for 25 hours under a current density of 10 mA/cm 2 and a temperature of 40 〇c. [Example 5 0.2 〇 33 g of the anode slime concentrated in Ag prepared in the above Example 4, placed in 4 ml of 35% hydrogen acid, dissolved at the boiling temperature for 3 〇 minutes, filtered and washed to obtain 0. 〇 428 g Dissolved Ag residue. [Example 6] Ag dissolved residue powder obtained in Example 5 (Ag 99.5%) and AgCl sink and additionally formed by reacting sodium hydroxide (NaOH) with formic acid (HCOOH) The Ag powders were mixed together and formed into a disk shape of 5 mm in diameter, followed by sintering at 75 〇 13 201217542 ° C for 1 hour to form a coarse Ag anode for Ag electrolytic refining. The exposed area of the coarse Ag anode made of Ag was adjusted to be 9 square centimeters. Electrolytic refining was carried out using a 500 ml polytetrafluoroethylene (PTFE) electrolytic bath. The coarse Ag anode made of Ag was placed in a filter cloth made of polypropylene (PP) and having a mesh of 500 to prevent electrolyte contamination. The cathode for electrolytic refining of a coarse Ag anode made of Ag is made of a titanium material having a purity of 99.9% or more and has an exposed area of 9 square centimeters. The electrolyte used herein was a hno3 solution containing 0.5 mol/liter of AgN03 and having a concentration of 0.5 mol/liter. Electrolytic refining was carried out for 2 hours under the conditions of a current density of 30 mA/cm 2 . As a result, it was confirmed that the amount of Ag electrodeposition was 2.172 gram and the current efficiency was 99.9% or more. Analysis of the Ag component under electrolytic refining revealed that the purity of Ag was 99.99% or more. [Experimental Example 1] With respect to the electrolytic refining in Comparative Examples and Examples 1 to 3, the relationship between the electrochemical dissolution/purification procedure and the cr concentration in the sulfuric acid electrolyte was confirmed. [Table 1] Hydrogen acid concentration Anodic dissolution amount (g) Electrodeposition (g) Anode soft mud (g) Current efficiency comparison example - 2.3987 1.8772 0.1818 84.7 Example 1 0.1 2.4048 1.8733 0.1872 84.5 Example 2 0.2 2.4022 1.9630 0.1837 88.6 Example 3 0.3 2.4017 2.0449 0.1792 92.2 As shown in Table 1, in the case of the comparative example, the amount of anodic dissolution was 2.3987 g, the amount of Sn electrodeposited on the platinum cathode plate was 1.8772 g, and the amount of anode fine mud formation 14 201217542 was 0.1818. Gram. The electrodeposited Sn exhibits a needle shape and has a purity of 99.9% or higher. The Ag content in the anode slime was 43.1% and the Ag enrichment ratio in the anode slime was 81.7%. Here, in the case of Sn2+ electrodeposition, the current efficiency was calculated to be 84.7%, and after standing for a while, a white Sn oxide sink was formed from the electrolyte. In the case of Example 1, the amount of anodic dissolution was 2.4048 g, the amount of Sn electrodeposited on the platinum cathode plate was 1.8733 g, and the amount of anode fine mud formed was 0.1872 g. The electrodeposited Sn exhibits a needle shape and has a purity of 99.9% or higher. The Ag content in the anode fine mud was 46.23% and the Ag enrichment ratio in the anode fine mud was 89.9%. Here, in the case of Sn2+ electrodeposition, the current efficiency was calculated to be 84.5%, and precipitation of the Sn oxide did not occur in the electrolyte even after being left for a while. In the case of Example 2, the amount of anodic dissolution was 2.4022 g, the amount of Sn electrodeposited on the platinum cathode plate was 1.9630 g, and the amount of anode fine mud formed was 0.1837 g. The electrodeposited Sn exhibits a needle shape and has a purity of 99.9% or higher. The Ag content in the anode fine mud was 48.6% and the Ag enrichment ratio in the anode fine mud was 92.9%. Here, in the case of Sn2+ electrodeposition, the current efficiency was calculated to be 88.6%, and precipitation of the Sn oxide did not occur in the electrolyte even after being left for a while. In the case of Example 3, the amount of anodic dissolution was 2.4017 g, the amount of Sn electrodeposited on the platinum cathode plate was 2.0449 g, and the amount of anode fine mud formed was 0.1792 g. The electrodeposited Sn exhibits a needle shape and has a purity of 99.9% or higher. The Ag content in the anode fine mud was 50.5% and the Ag enrichment rate in the anode fine mud was 94.2%. Here, in the case of Sn2+ electrodeposition, the current efficiency was calculated to be 92.2%, and precipitation of the Sn oxide did not occur in the electrolyte even after being left for a while. From the results of the above Examples 1 to 3 and 2, it can be seen that by adding C1+ to electricity 15 201217542, the precipitation of Sn oxide in the electrolyte can be prevented, and the Ag enrichment rate in the anode slime is improved. . The results of Examples 1 to 3 confirmed that the difficulty and/or repeatability of the existing method for extracting, separating, and purifying precious metals from waste solder can be overcome, and Sn or Ag can be efficiently and economically recovered. [Experimental Example 2] The relationship between the results of the electrochemical dissolution/purification procedure and the current density was analyzed under the conditions of temperature and electrolyte composition in Example 3. [Table 2] Content (%) 10 mA/cm 2 25 mA/cm 2 50 mA/cm 2 Ag 50.54 48.17 55.64 Sn 34.67 37.27 31.70 Cu 11.50 11.31 6.64 0 3.2 3.24 5.96 s 0.09 - 0.06 Cl - - - The results of Tables 2 and 3 above confirm the relationship between the composition change of the anode fine mud and the increase in current density. In addition, it can be seen that the voltage increases as the fine mud layer formed on the anode increases. Furthermore, it has been found that a preferred current density of 10 mA/cm 2 can be extended by prolonging the process holding time (i.e., holding time) by maximizing the voltage increase. [Experimental Example 3] The compositions of the anode fines obtained in Examples 4 and 5 and the composition of the Ag residue obtained from the anode fines after solid-liquid separation were analyzed. 201217542 As shown in Fig. 4, the electrodeposited Sn exhibits a needle shape and has a purity of 99.9% or higher. The Ag content in the anode fine mud was 47.4% and the Ag enrichment rate was 95%. Further, as shown in Fig. 5, the purity of the dissolved Ag residue of the anode fine mud was 99.5%. The filtrate was reacted with a 0.5 mol/liter NaCl solution to give 0.0702 g of AgCl precipitate having an Ag content of 75.3%. Since the total amount of Ag is 0.0957 g, 99.5% of Ag can be recovered. As described above, the method for recovering Sn or Ag from the Pb-free waste solder of the present invention overcomes the difficulty and reproducibility of the method of extracting, separating and purifying precious metals from the existing waste solder, and can efficiently and economically recover high purity. Sn or Ag. A method for recovering Sn or Ag from a non-Pb waste solder according to the present invention, which uses an electrolyte containing gas ions (Cl_) in electrolytic refining to prevent precipitation of Sn oxide, which is an increase in Sn or Ag in the related art. A problem with the recycling rate. In addition, since the Ag enrichment rate and the Sn electrodeposition rate in the anode fine mud are improved, the recovery rate of Sn or Ag is improved. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a method of recovering Sn or Ag from a Pb-free waste solder according to an embodiment of the present invention; FIG. 2 is a view showing an electrochemical example according to an embodiment of the present invention. The result of the relationship between the dissolution/purification procedure and the concentration of cr in the sulfuric acid electrolyte; FIG. 3 illustrates the results of the relationship between the electrochemical dissolution/purification procedure and the current density under the conditions of the predetermined temperature and composition of the electrolytic solution according to Example 3 of the present invention; Fig. 4 is a view showing an analysis result of the composition of the anode fine mud obtained in Example 4 of the present invention. The results of the analysis of the composition of the Ag residue obtained in Example 5 of the present invention are illustrated in Fig. 5 . [Main component symbol description] (none) 18