1293999 本發明係關於一種以含貴金屬之流體電鍍工作件之方法 及裝置。本發明特別適用於生產電路載體之製程。 為了電鍍工作件，若其表面不導電則表面首先必須以使 其導電之方法處理。為了此目的，工作件浸人含離^、離 子化或膠態鈀之溶液。離子鈀可更特定地以鹽之形式存 在，例如氯化鈀，其通常溶解在氫氯酸溶液中。離子化鈀 以錯合物存在，例如銨基吡啶錯合物。膠態鈀可含有多樣 之保護膠體，如由氯化錫（11)形成或由有機聚合物組成之 保濩膠體。吸收在工作件表面之鈀作為例如活化劑以引起 無電金屬沉積，其使一層導電層在表面上形成故之後表面 可以任何金屬電鍍。利用此法製造印刷電路板及其他電路 載體以及例如衛生設備、汽車及家具工業中之鍍金屬零件 及更特定之鍍路塑膠零件。 含虹溶液亦可用於形成導電層。在此直接電鍍法中，其 他金屬在免處理後沒有預先以無電金屬塗佈法形成金屬層 下電鍍。 在處理具不導電表面工作件中，部分含鈀溶液在先前浸 潰工作件由溶液取出時仍附著在工作件。附著之溶液一般 以水清洗。 已知之活化方法例如使用膠態鈀，一般使用含5 〇 _ 4〇〇毫 克/升鈀之洛液。在處理具一平方公尺幾何表面之塑膠零件 中’典型上吸收約5 -1 〇毫克之鈀。此量必須活化塑膠表 面。當欲處理工作件離開相符之加工站時，由浴中帶走每 平方公尺約0.2升之活化溶液且仍留在表面上。因此，對該 _80133-960119.doc _4· 本紙張尺度適用中國國家標準(CiJs) Α4規捧(210X297公爱) A7 B7 1293999 五、發明説明（2 ) 浴約10-50毫克鈀損失因為附著之溶液帶出加工浴，之後 清洗並轉移至廢水處理。 在沒有無電鍍金屬之直接電鍍非導體表面中亦可利用含 鈀溶液。在這些情沉中，溶液中需要高濃度之鈀（如400毫 克/升）。 在執行已知之直接金屬電鍍方法中，由加工溶液帶走之 鈀的量約50亳克/平方公尺。藉採取適當方法如預先吸收聚 電解質化合物至非導體表面，吸收之鈀粒子可由極低之值 增加至約5 0毫克/平方公尺之工作件表面。雖然如此，用於 溶液中約60-70%之鈀因帶出而損失。只有40-30%實際用 於將工作件表面電鍍金屬。 已知由加工溶液回收鈀之實例。如美國專利第4,078,918 號敎述一種回復之回收方法，如由含溶解或非溶解之麵之 種種材料回收鈀。材料首先以氧化劑處理破壞可能之有機 組分，之,後以氫氧化銨處理以形成胺錯合物。如此得到之 |巴錯化物其次以抗壞血酸還原，故鈀由加工液中以金屬形 式沉積並可過濾。 此外，在 Chemical Abstracts，1990:462908 HCAPLUS 之 「由膠態種溶液液回收免（"Reclamation of Palladium from colloidal seeder solutions ·’）」中救述一種在無電鍍金屬前 由膠態Pd/SnCl2回復鈀作為預處理之方法，在其中溶液通 空氣24小時故鈀將聚集。沉積物分離、乾燥及進一步加 工0 在 Chemical Abstracts, 1985:580341 HCAPLUS之「由氯化 80133-960119.doc _5_ 本紙張尺度適用中國國家樣準(c^s) A4規格(210 X 297公釐） 1293999 A7 B7 五、發明説明（3 ) 錫中膠態鈀之廢液回收鈀及氯化錫」中敘述一種藉在9 〇 〇c 添加金屬錫沉澱鈀之方法。 美國專利第4,435,258號揭示由用於活化隨後作為無電鍍 金屬方法之表面的耗盡浴回收麵之另一方法。活化液藉添 加氧化劑如過氧化氫使膠態鈀氧化成溶液隨後加熱溶.液破 壞殘留過氧化氬且之後由此溶液電鍵鈀至陰極上再加工。 在 Chemical Abstracts，1976:481575 HCAPLUS之「排出之 用於無電流金屬塗佈樹脂表面之活化液之膠態鈀含量的回 復」中’最後敘述一種由Pd/SnCl2得到免之方法，其！巴藉 添加濃硝酸沉澱並過濾。 DE 100 24 239 C1敘述一種藉將工作件與膠體溶液接觸 以細膠體溶液電鍍工作件之方法，根據此法鈀在使用膠體 後藉膜濾心之方法由膠體溶液分離鈀膠體粒子回收鈀。可 使用例如陶鸯製之材料過濾。膜之孔徑大小為2〇〇至1〇,〇〇〇 道爾頓。， 以免膠體溶液之電鍍工作件之先前技藝方法複雜且昂貴 的。 本發明面對之基本問題為避免已知方法之缺點並找出以 含有至少一種貴金屬之流體電鍍工作件且可在低成本下執 行之方法。應只需要小量之額外化學藥品執行此法。此 外’此法應包括很小之消耗能量及時間且應更特別地要求 低維護。 此問題藉根據申請專利範圍第i項之方法及根據申請專利 範園第15項之裝置克服。本發明之較佳具體實施例在附屬 80133-960119.doc U張尺度適財目目家鮮㈣s) A4«^(21GX 297公------ 1293999 A7 B7 五、發明説明（4 申請專利範圍中所指示。 根據本發明之方法以流體電鍍工作件，該流體含至少一 種貴金屬，此法包括將工作件與流體接觸。為了由流體回 收貴金屬之目的，該流體在電鍍工作件後透過至少一種陶 資膜過濾由流體分離貴金屬，陶資膜攄心之排出孔大小超 過1〇,〇〇〇道爾頓。由於過濾貴金屬由流體分離。 對電鍍，具流體之任何處理意指直接改變工作件之表 面，此流體必須含有貴金屬。可是在其中不包括以聚合物 塗層塗佈工作件之方法，特別是塗料之方法。 欲塗之工作件包括金屬工作件、非金屬工作件及由金屬 及非金屬材料組成之工作件。工作件可具有所有可相像之 形式且打算做所有可想像的利用。較佳之王作件^生產 电路載體《半塗工產物，更特別地是生產印刷電路板及混 合電路載體如多晶片模組。 可由相i符足流體分離之貴金屬為週期表元素之第〗及第 VIH族之所有元素，即特別是Ru、Rh、pd〇s、ir、 、 g及Au。本發明較佳地係關於藉含鈀流體電鍍 《處理工作件之方法。 更特別地，流體可為溶液。當貴金屬以離子或離子化形 巧在時這是更特別之情況。對離子形式之貴金屬，溶解 中或在促進孩鹽溶解之另—溶射之貴金屬鹽為更特 ，。=離子化形式之貴金屬’貴金屬錯合物為其所指特 =合配位基之貴金屬錯合物。錯合物可為不帶 何或以離子形式存在。流體可為膠體形式存在，特別是 80133-960119.doc 本紙張尺目家料(國71^(21〇 X 29·= 12939991293999 The present invention relates to a method and apparatus for electroplating a workpiece with a noble metal-containing fluid. The invention is particularly applicable to the process of producing circuit carriers. In order to plate a workpiece, if the surface is not electrically conductive, the surface must first be treated in a manner that makes it conductive. For this purpose, the workpiece is impregnated with a solution containing lithium, ionized or colloidal palladium. The ionic palladium may more particularly be present in the form of a salt, such as palladium chloride, which is usually dissolved in a hydrochloric acid solution. The ionized palladium is present as a complex, such as an ammonium pyridine complex. Colloidal palladium can contain a variety of protective colloids, such as a colloidal colloid formed of or consisting of tin chloride (11). Palladium absorbed on the surface of the workpiece acts as, for example, an activator to cause electroless metal deposition, which causes a layer of conductive layer to form on the surface so that the surface can be plated with any metal. This method is used to manufacture printed circuit boards and other circuit carriers as well as metallized parts such as sanitary equipment, automotive and furniture industries, and more specifically plated plastic parts. The iridescent solution can also be used to form a conductive layer. In this direct plating method, other metals are not plated under the metal layer by electroless metal coating before the treatment. In processing a workpiece having a non-conducting surface, a portion of the palladium-containing solution remains attached to the workpiece while the previous impregnation workpiece is removed from the solution. The attached solution is usually washed with water. Known activation methods such as the use of colloidal palladium generally use a solution containing 5 〇 _ 4 〇〇 milligrams per liter of palladium. Typically, about 5-1 milligrams of palladium is absorbed in a plastic part having a geometric surface of one square meter. This amount must activate the plastic surface. When the workpiece is to be processed away from the matching processing station, about 0.2 liters of activation solution per square meter is carried from the bath and remains on the surface. Therefore, the _80133-960119.doc _4· This paper scale applies the Chinese national standard (CiJs) Α 4 regulations (210X297 public) A7 B7 1293999 V. Invention description (2) Bath about 10-50 mg palladium loss due to adhesion The solution is taken out of the processing bath, then washed and transferred to wastewater treatment. Palladium-containing solutions can also be utilized in direct electroplated non-conductor surfaces without electroless metal. In these conditions, a high concentration of palladium (e.g., 400 mg/L) is required in the solution. In carrying out the known direct metal plating process, the amount of palladium carried away by the processing solution is about 50 g/m2. By appropriate means such as pre-absorption of the polyelectrolyte compound to the non-conductor surface, the absorbed palladium particles can be increased from very low values to the surface of the workpiece of about 50 mg/m 2 . Nonetheless, about 60-70% of the palladium used in the solution is lost due to carryover. Only 40-30% is actually used to plate the surface of the workpiece with metal. An example of recovering palladium from a processing solution is known. A recovery method for recovery, such as recovery of palladium from various materials containing dissolved or insoluble surfaces, is described in U.S. Patent No. 4,078,918. The material is first treated with an oxidizing agent to destroy the possible organic components, which are then treated with ammonium hydroxide to form an amine complex. The thus obtained bromine is secondarily reduced with ascorbic acid, so that palladium is deposited in a metal form in the working fluid and can be filtered. In addition, in Chemical Abstracts, 1990: 462908 HCAPLUS, "Reclamation of Palladium from colloidal seeder solutions (')", one of which was recovered from colloidal Pd/SnCl2 before electroless metal. Palladium is used as a pretreatment method in which palladium will aggregate when the solution is passed through air for 24 hours. Sediment separation, drying and further processing 0 in Chemical Abstracts, 1985: 580341 HCAPLUS "from chlorination 80133-960119.doc _5_ This paper scale applies to China National Standard (c^s) A4 size (210 X 297 mm) 1293999 A7 B7 V. INSTRUCTIONS (3) Recovery of palladium and tin chloride from waste liquid of colloidal palladium in tin" describes a method for depositing palladium by adding metallic tin at 9 〇〇c. Another method for recovering a depleted bath recovery surface for a surface that is subsequently used as an electroless metal removal process is disclosed in U.S. Patent No. 4,435,258. The activation liquid is oxidized to a solution by adding an oxidizing agent such as hydrogen peroxide to a solution and then heated to dissolve the residual argon peroxide, and then the solution is palladium-to-cathed by the solution. In Chemical Abstracts, 1976: 481575 HCAPLUS, "Repeating the recovery of the colloidal palladium content of the activation liquid for the surface of the currentless metal coating resin", a method for obtaining Pd/SnCl2 is finally described, which is! The bar was added with concentrated nitric acid and filtered. DE 100 24 239 C1 describes a method of electroplating a working piece with a colloidal solution by contacting a working piece with a colloidal solution. According to this method, palladium is used to separate palladium colloidal particles from a colloidal solution to recover palladium by using a membrane filter after the colloid is used. It can be filtered using materials such as ceramics. The pore size of the membrane ranges from 2 〇〇 to 1 〇, 〇〇〇 Dalton. The prior art method of electroplating the working piece of the colloidal solution is complicated and expensive. The basic problem faced by the present invention is to avoid the disadvantages of known methods and to find a method of electroplating a workpiece with a fluid containing at least one precious metal and which can be performed at low cost. Only a small amount of additional chemicals should be required to perform this method. In addition, this method should include a small amount of energy and time and should require more maintenance. This problem is overcome by the method of claim i and the device according to item 15 of the patent application. A preferred embodiment of the present invention is attached to the article 80133-960119.doc U-scale commercial resources (four) s) A4 «^ (21GX 297 public ------ 1293999 A7 B7 five, invention description (4 patent application) In accordance with the method of the present invention, the fluid is electroplated with a working member comprising at least one precious metal, the method comprising contacting the working member with a fluid. For the purpose of recovering the precious metal from the fluid, the fluid passes through at least the electroplated workpiece. A ceramic membrane filter separates precious metals by fluid, and the pore size of the ceramic membrane is more than 1 〇, 〇〇〇 Dalton. Since the precious metal is separated by fluid separation. For electroplating, any treatment with fluid means direct change of work. The surface of the piece must contain precious metals. However, the method of coating the working piece with a polymer coating, especially the method of coating, is not included. The working piece to be coated includes metal working piece, non-metal working piece and metal And the working piece composed of non-metallic materials. The working piece can have all the similar forms and is intended to be used for all imaginable use. Semi-coating products, more particularly producing printed circuit boards and hybrid circuit carriers such as multi-wafer modules. The precious metal which can be separated by the fluid is the element of the periodic table element and all elements of the VIH group, that is, especially Ru, Rh, pd〇s, ir, g, and Au. The present invention is preferably directed to a method of treating a workpiece by electroplating with a palladium-containing fluid. More particularly, the fluid can be a solution. When the noble metal is ionized or ionized This is a more special case. In the case of precious metals in the ionic form, the precious metal salt in the dissolution or in the dissolution of the other salt is more special. The ionized form of the noble metal 'precious metal complex is A noble metal complex of a specific ligand; the complex may be in the form of no or any ionic form. The fluid may be in the form of a colloid, especially 80133-960119.doc. 71^(21〇X 29·= 1293999
元素貴金屬之膠體。 含貴金屬之流體可為處理工作件乏加工流體或清洗流 體。對加工流體意指改變工作件表面性質之流體，如塗佈 流體，包括活化流體、洗淨流體、蝕刻流體或類似物◊比 較上’清洗流體只在以加工流體處理工作件後作為清除仍 附著在工作件表面之加工流體。 在使用電鍍工作件之流體後，貴金屬以至少一個陶瓷膜 滤心過滤。這意指流體首先用於電鍍且只在後來為了回收 其含有之貴金屬之目的時過濾。流體可藉例如噴灑、噴射 淹沒或***接觸工作件，收集由工作件滴下之流體之後收 集之流體立刻以膜濾心處理。然而收集之流體亦可首先留 在儲存槽，由此送回工作件。在此情況中，流體可在收集 一段預定之時間後以膜濾心處理（間斷法），或部分流體可 連續地由儲存槽分接出並轉移至膜濾心（連續法）^為了達 到此情況，中儲存槽内無變化之充滿狀態，新加工流體永遠 以每單位時間之量等於每單位時間透過膜濾心流體之量導 入儲存槽。工作件亦可用在處理容器内之加工流體以浸潰 之方式接觸。在此情況中，加工流體在使用後在收集一段 預定期間後以膜濾心處理（間斷法），或部分流體可連績地 由儲存槽分接出並轉移至膜濾心（連續法）^ 本發明之方法允許以簡單之方法並以小量消耗化學品、 能量及時間以及很小之維護、在連續條件下由排出之加工 液明顯的分離貴金屬完成。更特別地其允許在含鈀之分離 後再生用盡之加工液，故整個把可循環至製程中。 80133-960119.doc _8. 本紙張尺度適用中國國家標準(C泣S) A4規袼(210X297公釐) A7 B7 1293999 五、發明説明（6 ) 在 Chemical Abstracts，1990:462908 HCAPLUS 中敘述由膠 態Pd/SnCl2回復鈀之方法下，本發明方法有分餾物完全分 離之優點，然而Chemical Abstracts中敘述之沉澱法中非可 忽略之鈀氧化形成二價（其可溶之狀態），故其不能完全藉 過滤由溶液中分離。因此，這部分之把不能回收且將損失 本發明方法對 Chemical Abstracts，1985:580341 HCAPLUS 敘述之方法的另一優點為不需要相當地消耗像金屬錫一般 之化學藥品及能量且時間與以加熱膠體溶液為目的之已知 方法要求相當。 根據本發明之方法對美國專利第4,435,258號亦有實質之 優點，即鈀可幾乎完全由溶液移除，然而對根據美國專利 第4,435,258號，僅可達到極低之電流效率，特別是當鈀濃 度低時（這在長期電解後發生）。因此，其非常複雜或根本 不可能以先前技藝之方法完全移除鈀。 比較 Chemical Abstracts，1976:481575 HCAPLUS 中敘述之 方法，根據本發明之方法及裝置特別適合連續操作。此 外，在此公開案中之方法強制地需要添加化學藥品。 令人驚訝地，與孔排出大小明顯超過1〇,〇〇〇道爾頓之膜 濾心之性能與德國專利100 24 239 c 1所指示一樣且根據此 膠態把膠體溶液之免粒子透過滤心’孔排出大小如20,000 道爾頓之陶瓷濾心的分離性質證明對鈀極佳。關於這點， 參考實例1之試驗1及2。 根據本發明之方法及裝置對已知之方法及裝置有下面之 80133-960119.doc -9- 本紙張尺度適用中國國家樣準(C校S) A4規格(210X297公釐） 1293999 A7 B7 ___ 五、發明説明（7、 ~ 優點： a ·貴金屬（特別是鈀）可由離子、離子化及膠態溶液以只有 一個裝置回收。其不需要使用幾個相配之裝置。結果，溶 液可在再生前混合並收集。同樣結果，亦應用於加工及清 洗流體：具高濃度貴金屬之加工流體可與含極低濃度貴金 屬之清洗流體混合，之後一起加工。 b.可利用對化學藥品及溫度效應有大抵抗能力之陶瓷膜濾 心因為貴金屬之分離以大孔之陶瓷膜濾心亦成功^維護少 為濾心不需要經常清潔之結果。陶瓷膜濾心亦具長的耐久 壽命。此外，貴金屬不吸收在膜材料上。 c ·欲處理之流體以非常簡單之方法再加工。其不需要在如 保護氣氣下工作以防止膠癌粒子溶在流體中。 以鈀為基礎之膠態活化劑包括由保護塗層（保護膠）圍繞 之鈀粒子。使用高解析度穿透式電子顯微鏡（HTEM)及原子 力顯微繞（AFM)之試驗顯示把粒子之直徑至少2.5奈米。平 均粒子直徑為約4奈米，與粒子之高斯分怖一致。在試驗中 得到在以膠態活化劑處理工作件後之清洗流體，測定顯示 具最大大小約1 8奈米以及較小粒子（2至1 8奈米）之粒子之 寬粒子大小分佈。 在實際之利用中，膠體溶液為酸性的（常為高氫氣酸性 的），且含氯離子以及可能地氧化態（II)及（I v)之錫或有 機、聚合安定劑像明膠或聚乙烯基吡嘻酮及還原劑。除了 聚合物（小量利用）之外，所有其他在此所含之物質為離 子。假定這些離子構成物比鈀粒子小。 80133-960119.doc -10- 本紙張尺度適用中國國家標準(C校S) A4規#(21〇Χ297公羡) A7 B7 1293999 五、發明説明（8 ) 令人驚許地，鈀粒子可藉包括不同孔隙度之適當膜滤心 之方法非常選擇性及完全地由這些膠體溶液移除，雖然在 含錫膠態溶液之情況中，同時存在之錫為高濃度（一般超過 7 0倍免濃度）且雖然已知錫化合物形成不易過濾之膠態溶 液。 對於超過濾，已試驗由種種材料製造之多種形式膜。試 驗顯示在選擇膜濾心之所有問題較特別的是其對含貴金屬 且可含例如1 5重量百分比之氫氣酸足夠安定。 為了分離鈀膠體粒子，可利用排出孔大小約15,000道爾 頓至約25,000道爾頓之陶瓷膜滤心，更特別地排出孔大小 約17,500道爾頓至約22,500道爾頓而以約20,000道爾頓最 佳。 較佳利用之陶瓷膜濾心由含氧化鋁（特別是α - Al2 03)、 二氧化鈦及可能之二氧化結之陶瓷材料製造。理論上，亦 可利用其他濾心材料。通常，濾心材料置於提供濾心要求 機械安定性之高度多孔支撐體上。此支撐體可由例如α -αι2ο3或SiC(碳化矽）組成。 濾心外形可為盤或管之形式。在第一種情況中，流動朝 向盤，约垂直其表面，該流動以半徑方向脫離。在二盤表 面間建立壓差，故透過可滲透該盤。若濾心之形狀為管 形，流體以軸向運送通過該管，在管之内空間及外空間間 建立壓力。結果，透過可滲透管壁如由管之内體積至管之 外空間。這第二法稱為動態過滤。在此一情況中，貴金屬 維持在管之内空間，然而由貴金屬大量釋放之流體經管壁 __80133-960119.doc ___-11-_,___ 本紙張尺度適用中國國家標準(C泣S) A4規辂(210X297公釐） 1293999 Δ A / ____Β7_ 五、發明説明（9 ) 由管之内體積透過至管外之空間。 一些流體可直接過濾不需任何額外之預處理。在此情況 中，以陶瓷膜濾心得到極好之結果。 在一些情況中，欲再加工之流體首先經化學預處理。在 已作電鍍使用後經膜濾心過濾前，流體因此目的與適合改 ’支至少一種以此法在過滤時幾乎完全留下之貴金屬的化學 物質混合。假定藉加入這些化學物質，貴金屬之粒子大小 以使含貴金屬之粒子不通過膜濾心之孔之方式改變。為了 此一目的，當粒子大小符合高斯分佈時其應足以調整平均 粒子大小至超過約1 0奈米之值。在此情況中，排出孔大小 超過10,000道爾頓之膜濾心已經留下幾乎整個量之貪金屬 於濃縮液中。因此當使用具較大排出孔大小之膜濾心時可 藉加入這些化學物質設定較大之粒子。 若免以離子及/或離子化形式存在溶液中，液體可以選自 還原劑、硫化合物、硒化合物及碲化合物之化學物質混 合。預處理用之化學物質以選自氫化硼、胺硼烷、次嶙酸 鹽、無機硫化物及有機硫化合物最佳，特別是二甲基二硫 代胺基甲酸鹽、硫化物、氫化硼（如四氫硼酸鹽）及次嶙酸 鹽之鹼土及銨鹽。可慮之有機硫化合物為更特別之有機化 合物，其中硫鍵結至一或二個碳原子形成單键或雙键，即 例如硫醇、硫化物、二硫化物及多硫化物、硫醯胺及破 趁0 若鈀以膠態形式存在流體中，使用pH調整劑作為化學物 質。流體與pH調整劑以使pH範圍為3至12之方式混合。 80133_960119.doc_-12-__. ____ 本紙張尺度適用中國國家標準(C泣S) A4規袼(210X297公釐） 1293999The colloid of elemental precious metals. The noble metal-containing fluid can be used to treat the working fluid or the cleaning fluid. By process fluid is meant a fluid that changes the surface properties of the workpiece, such as a coating fluid, including an activating fluid, a cleaning fluid, an etching fluid, or the like. In contrast, the cleaning fluid is only attached as a purge after processing the workpiece with the processing fluid. Processing fluid on the surface of the workpiece. After the fluid of the electroplated workpiece is used, the precious metal is filtered through at least one ceramic membrane filter. This means that the fluid is first used for electroplating and is only filtered later for the purpose of recovering the precious metals it contains. The fluid may be submerged or blasted to contact the workpiece by, for example, spraying, spraying, and the fluid collected after collecting the fluid dripped by the workpiece is immediately treated with a membrane filter. However, the collected fluid can also be left in the storage tank first, thereby returning the work piece. In this case, the fluid may be treated by a membrane filter after a predetermined period of time (intermittent method), or part of the fluid may be continuously separated from the storage tank and transferred to the membrane filter (continuous method). In the case where there is no change in the full state of the storage tank, the new processing fluid is always introduced into the storage tank in an amount equal to the amount of fluid per unit time per unit time. The workpiece can also be contacted by impregnation with the processing fluid within the processing vessel. In this case, the processing fluid is treated by the membrane filter after being used for a predetermined period of time after the use (intermittent method), or part of the fluid can be tapped out from the storage tank and transferred to the membrane filter (continuous method)^ The process of the present invention allows for the simple separation of precious metals from the discharged process fluids in a simple manner and with a small amount of chemical, energy and time, and minimal maintenance under continuous conditions. More specifically, it allows the spent working fluid to be regenerated after the separation of the palladium-containing separation, so that the entire process can be recycled to the process. 80133-960119.doc _8. This paper scale applies to Chinese national standards (C weep S) A4 gauge (210X297 mm) A7 B7 1293999 V. Description of invention (6) Described in colloidal state in Chemical Abstracts, 1990: 462908 HCAPLUS The method of the present invention has the advantages of complete separation of the fraction by Pd/SnCl2 recovery of palladium. However, the non-negligible palladium oxidation in the precipitation method described in Chemical Abstracts forms divalent (the soluble state), so it cannot be completely Separated from the solution by filtration. Therefore, another advantage of this method that cannot be recovered and will lose the method of the present invention described in Chemical Abstracts, 1985: 580341 HCAPLUS is that it does not require considerable consumption of chemicals and energy like metal tin and time to heat the colloid. Known methods for the purpose of the solution are equivalent. The method according to the invention also has the substantial advantage of U.S. Patent No. 4,435,258, that is, palladium can be removed almost completely from the solution, however, according to U.S. Patent No. 4,435,258, only very low current efficiencies can be achieved, especially when palladium concentration Low (this happens after long-term electrolysis). Therefore, it is very complicated or impossible to completely remove the palladium by the method of the prior art. Comparing the methods described in Chemical Abstracts, 1976: 481575 HCAPLUS, the method and apparatus according to the present invention are particularly suitable for continuous operation. Moreover, the method in this publication forcibly requires the addition of chemicals. Surprisingly, the pore discharge size is significantly more than 1 〇, the performance of the membrane filter of 〇〇〇Dalton is the same as that indicated in German Patent 100 24 239 c 1 and the particle-free filtration of the colloidal solution is filtered according to this colloidal state. The separation properties of the ceramic filter core with a pore size of 20,000 daltons proved to be excellent for palladium. In this regard, refer to Tests 1 and 2 of Example 1. According to the method and device of the present invention, the known methods and devices have the following 80133-960119.doc -9- The paper scale is applicable to the Chinese national standard (C school S) A4 specification (210X297 mm) 1293999 A7 B7 ___ V. DESCRIPTION OF THE INVENTION (7, ~ Advantages: a · Precious metals (especially palladium) can be recovered by ion, ionized and colloidal solutions in only one device. It does not require the use of several matching devices. As a result, the solution can be mixed before regeneration and The same result is also applied to the processing and cleaning fluid: the processing fluid with high concentration of precious metal can be mixed with the cleaning fluid containing very low concentration of precious metal, and then processed together. b. It can be used with great resistance to chemicals and temperature effects. The ceramic membrane filter core is also successful because of the separation of the precious metal with the large-hole ceramic membrane filter. The maintenance of the filter core does not require frequent cleaning. The ceramic membrane filter also has a long durability life. In addition, the precious metal is not absorbed in the membrane. On the material c. The fluid to be treated is reprocessed in a very simple way. It does not need to work under protective gas to prevent the colloidal particles from being dissolved in the fluid. Palladium-based colloidal activators include palladium particles surrounded by a protective coating (protective gel). High-resolution transmission electron microscopy (HTEM) and atomic force microscopy (AFM) tests have shown that the diameter of the particles is at least 2.5 nm. The average particle diameter is about 4 nm, which is consistent with the Gaussian particle of the particle. In the test, the cleaning fluid after treating the workpiece with the colloidal activator was obtained, and the measurement showed a maximum size of about 18 nm and The broad particle size distribution of particles of smaller particles (2 to 18 nm). In practical use, the colloidal solution is acidic (often highly hydrogen acidic) and contains chloride ions and possibly oxidation states (II And (I v) tin or organic, polymeric stabilizers such as gelatin or polyvinylpyrrolidone and reducing agents. All but the polymer (small amount of use) is an ion. These ion compositions are smaller than palladium particles. 80133-960119.doc -10- This paper scale applies to Chinese national standards (C school S) A4 regulation # (21〇Χ297 public) A7 B7 1293999 V. Invention description (8) Order Surprisingly, palladium particles can be borrowed The method of arranging the appropriate membranes with different porosities is very selective and completely removed by these colloidal solutions, although in the case of tin-containing colloidal solutions, the simultaneous presence of tin is high (generally more than 70 times the concentration) And although tin compounds are known to form colloidal solutions that are difficult to filter. For ultrafiltration, various forms of membranes have been tested which are manufactured from a variety of materials. Tests have shown that all of the problems in selecting membrane filters are particularly noble and precious. Hydrogen acid containing, for example, 15 weight percent is sufficiently stable. To separate the palladium colloidal particles, a ceramic membrane filter having a discharge orifice size of from about 15,000 Daltons to about 25,000 Daltons can be utilized, more particularly a discharge orifice size of about 17,500 Dao. It is about 22,500 Daltons and is about 20,000 Daltons. A preferred ceramic membrane filter is made of a ceramic material containing alumina (especially α-Al2 03), titanium dioxide and possibly a dioxide junction. In theory, other filter materials can also be used. Typically, the core material is placed on a highly porous support that provides mechanical stability to the filter. This support may be composed of, for example, α -αι 2ο 3 or SiC (ruthenium carbide). The shape of the filter can be in the form of a disc or tube. In the first case, the flow is directed toward the disk, about perpendicular to its surface, and the flow is detached in a radial direction. A pressure difference is established between the two disks, so that the disk can be penetrated through. If the shape of the filter is tubular, fluid is transported axially through the tube, creating a pressure between the space within the tube and the outer space. As a result, the permeable tube wall passes through the volume inside the tube to the space outside the tube. This second method is called dynamic filtering. In this case, the precious metal is maintained in the space inside the tube, but the fluid released by the precious metal is discharged through the tube wall __80133-960119.doc ___-11-_, ___ This paper scale applies to the Chinese national standard (C weep S) A4 Specification (210X297 mm) 1293999 Δ A / ____Β7_ V. Description of the invention (9) The space inside the tube is transmitted to the space outside the tube. Some fluids can be directly filtered without any additional pretreatment. In this case, excellent results were obtained with a ceramic membrane filter. In some cases, the fluid to be reprocessed is first chemically pretreated. The fluid is therefore intended to be mixed with a chemical suitable to modify at least one noble metal which is almost completely left by the filtration in this manner, prior to filtration through the membrane core after it has been used for electroplating. It is assumed that by adding these chemicals, the particle size of the noble metal is changed in such a manner that the particles containing the noble metal do not pass through the pores of the membrane filter. For this purpose, the particle size should be sufficient to adjust the average particle size to a value above about 10 nm when the particle size is Gaussian. In this case, the membrane filter having a discharge orifice size exceeding 10,000 Daltons has left almost the entire amount of the metal in the concentrate. Therefore, when using a membrane filter having a large discharge pore size, it is possible to add larger particles by adding these chemicals. If free from ion and/or ionized forms, the liquid may be selected from the group consisting of reducing agents, sulfur compounds, selenium compounds, and ruthenium compounds. The chemical substance for pretreatment is preferably selected from the group consisting of boron hydride, amine borane, sulfonate, inorganic sulfide and organic sulfur compound, especially dimethyldithiocarbamate, sulfide, boron hydride. (such as tetrahydroborate) and alkaline earth and ammonium salts of hypobromite. It is contemplated that the organosulfur compound is a more specific organic compound in which sulfur is bonded to one or two carbon atoms to form a single bond or a double bond, ie, for example, a mercaptan, a sulfide, a disulfide, and a polysulfide, thiourethane. And breaking 趁0 If palladium is present in the fluid in a colloidal form, a pH adjuster is used as the chemical. The fluid is mixed with the pH adjuster in a manner that allows the pH to range from 3 to 12. 80133_960119.doc_-12-__. ____ This paper scale applies to Chinese national standards (C weep S) A4 gauge (210X297 mm) 1293999
在二種情況中，得到非常適合分離貴金屬之溶液，在此 情況中為分離鈀。 下列優點由本發明之改良產生·· a.預處理非常簡單。其足以將含貴金屬之流體分別與要求 之物質或與p Η調整劑。 b ·消耗頟外化學藥品極少。為了加工由處理有機免錯合物 產生之200升清洗之水（7亳克/升之鈀”只需要了」亳升含 467克/升一甲基二硯代胺基甲酸鈉之溶液。若欲加工由處 理鈀膠體（有機保護膠體，25亳克/升pd)產生之清洗水， 只要0.5升之432克/升之NaOH水溶液將足夠。 由產生本發明之觀察及試驗能推論藉膜滤心由请洗流體 及/或加工流體回收貴金屬為可行的。為了此目的 a.工作件與含麵加工流體接觸， 後，仍附著在工作件之表面的加工流體以清洗流體 移除，及 c ·加工流體及/或清洗流體通過（在壓力下較佳）至少一 個過濾用之陶瓷膜濾心，通過至少一個膜濾心之透過 流體而未通過至少一個陶資膜濾心之流體為濃縮流 體。 在以含鈀流體處理後，（以非導電材料製造較佳）工作件 在合適之裝置中藉以清洗流體清洗，其經由浸潰、淹沒或 較佳地以噴灑該清洗流體至該工作件上以保持清洗流體之 體積愈小愈好。其次清洗流體藉壓力幫浦通過陶資膜減心 處理，該濾心留下把粒子並讓清洗液透過。此透過液^後In either case, a solution which is very suitable for the separation of the noble metal is obtained, in this case the separation of palladium. The following advantages are produced by the improvement of the present invention. a. Pretreatment is very simple. It is sufficient to separate the precious metal-containing fluid with the desired material or with the p Η conditioner. b · Very little extra chemical is consumed. In order to process 200 liters of washing water (7 g/l palladium) produced by treating the organic error-free compound, it is only necessary to soar up a solution containing 467 g/l of monomethyldidecylcarbamate. Processing the washing water produced by treating the palladium colloid (organic protective colloid, 25 g/l pd), as long as 0.5 liter of 432 g/liter of NaOH aqueous solution will suffice. From the observation and test of the present invention, the film can be inferred. It is feasible to recover the precious metal from the washing fluid and/or the processing fluid. For this purpose, a. the working piece is in contact with the surface-containing processing fluid, and then the processing fluid still attached to the surface of the working piece is removed by the cleaning fluid, and c· The processing fluid and/or the cleaning fluid pass (preferably under pressure) at least one ceramic membrane filter for filtration, and the fluid that has passed through the at least one membrane filter and not passed through at least one of the ceramic membrane cores is a concentrated fluid. After treatment with a palladium-containing fluid, the workpiece (preferably made of a non-conductive material) is cleaned in a suitable apparatus by a cleaning fluid which is impregnated, submerged or preferably sprayed onto the workpiece. After maintaining the cleaning fluid volume as small as possible. Second, the cleaning fluid through the pump by the pressure reducing heart ceramic membrane owned treatment, leaving the core of the particle filter and allow cleaning solution to pass through. This permeate ^
80133-960119.doc _"13 ~ 本纸張尺度適用中國國家標準(C资S) A4規格(21〇 X 297公董) 1293999 〜 A7 _________Β7 五、發明説明（1彳） 轉移至廢水處理。 在以膜滤心處理前，加工流體及/或清洗流體可與化學物 質如還原劑、硫化合物、硒化合物、碲化合物或pH調整 劑。 在本發明之特佳具體實施例中，只有清洗流體或含以最 南5體積百分比之加工流體較佳之清洗流體以膜濾心（在壓 力下較佳）處理。工作件與新清洗液接觸，永遠有每單位時 間預定量之新清洗液。更特別地每單位時間形成透過液之 量可調整至約等於每單位時間與工作件接觸之清洗液的 量。結果’在加工設備中達到靜止條件：輸送到工作件之 新清洗流體之量正好與由裝置流出之透過流體之量相同， 得到之結果為固定流動之物質。當然這只在若加入化學物 質之量可忽略且沒有額外影響變數影響製程下成立。實際 上，清洗流體之蒸發可成為一個主要的部分。 以均‘分散之金屬或金屬化合物之形式的濃縮液存在（如 以PdS分散）之留下的鈀可回收。留下的鈀可例如溶解、轉 變成氯化鈀並利用來合成新含鈀加工流體或作其他應用。 含把之濃縮液亦可在壓榨之濾心中濃縮至乾燥。為了此目 的，來自膜濾心之濃縮流體集中至在濃縮沉積中已形成含 鈀淤漿之容器中，淤漿懸浮液集中至壓榨之濾心。由壓榨 之濾心得到之含鈀濾餅可用作製造純鈀及鈀化合物乏基底 物質。 根據本發明之以含至少一種貴金屬之流體電鍍工作件之 裝置典型上提供將工作件接觸流體之方法，以及支撐工作 80133-960119.doc -H- 本紙張尺度適用中國國家標準(C泣S) A4规袼(210X 297公釐) 1293999 、 A780133-960119.doc _"13 ~ This paper scale applies to Chinese national standard (C capital S) A4 specification (21〇 X 297 DON) 1293999 〜 A7 _________Β7 V. Invention description (1彳) Transfer to wastewater treatment. The processing fluid and/or cleaning fluid may be associated with a chemical such as a reducing agent, a sulfur compound, a selenium compound, a hydrazine compound or a pH adjuster prior to treatment with a membrane filter. In a particularly preferred embodiment of the invention, only the cleaning fluid or the preferred cleaning fluid containing up to 5 volume percent of the processing fluid is treated with a membrane filter (preferably under pressure). The work piece is in contact with the new cleaning solution and there is always a predetermined amount of new cleaning solution per unit time. More specifically, the amount of permeate formed per unit time can be adjusted to be approximately equal to the amount of cleaning liquid contacted with the workpiece per unit time. As a result, the stationary condition was reached in the processing equipment: the amount of the new cleaning fluid delivered to the workpiece was exactly the same as the amount of the permeated fluid flowing out of the apparatus, and the result was a fixed-flowing substance. Of course, this is only true if the amount of chemical added is negligible and there is no additional influence on the variable influence process. In fact, evaporation of the cleaning fluid can be a major part. Palladium remaining in the presence of a concentrated metal or metal compound (e.g., dispersed in PdS) can be recovered. The remaining palladium can be, for example, dissolved, converted to palladium chloride and utilized to synthesize a new palladium-containing processing fluid or for other applications. The concentrate containing the concentrate can also be concentrated to dryness in the press filter. For this purpose, the concentrated fluid from the membrane filter is concentrated in a vessel in which a palladium-containing slurry has been formed in the concentrated deposition, and the slurry suspension is concentrated to the press filter. The palladium-containing filter cake obtained from the press filter can be used as a substrate for the production of pure palladium and palladium compound. The apparatus for electroplating a workpiece with a fluid containing at least one precious metal according to the present invention typically provides a method of contacting the workpiece with a fluid, and supporting work 80133-960119.doc - H- This paper scale applies to the Chinese National Standard (C Cr) A4 gauge (210X 297 mm) 1293999, A7
件之方法。 流體與工作件接觸之方法如嘴灑、噴射、 工或清洗流體至工作件表面上之噴頭。此安排：或放出加 成體將在高流動速度達到該表面或當需要流^例如當 ΐ!時。在本發明之另-具體實施例中，接觸 备态，其中之加工流體將拋棄且工作件在其中浸清。、、 工作件之支撐法亦可包括在多種形式中··工^件可用例 如夹鉗、螺絲鉗、火鉗或螺絲固定之傳統方式保存。此 外，工作件亦可簡單以水平之位置在輥、輪或圓柱上I 持、輸送及處理或其可夾在其間。 除了前面提及之特徵外，裝置亦包括由流體分離至少一 種貴金屬之設施。此設施包括至少一個排出孔大小超過 10,000道爾頓之陶瓷膜。此設施尚包括輸送流體至至少一 個膜之幫浦及將流體由接觸工作件之處導引至至少一個陶 瓷膜之滅,體導管0對幫浦，其指非馬達操作之任何幫濟或 亦指簡單藉重力輸送流體者。 根據上面提供之解釋，由流體分離貴金屬之設施尚有混 合設施。在此混合設施中，來自流體與工作件接觸處之流 體可與化學物質混合。為此目的，可利用化學反應技術中 任何已知之傳統混合設施，如攪拌設施及流動反應器中之 混合區。 此外，由流體分離貴金屬之設施亦有多相分離單元’在 其中由流體分離時產生且來自由流體分離貴金屬之設施的 於漿可沉積。此形式之多相分離單元由例如沉降箱形成’ 80133-960119.doc _15_ 本紙張尺^適用中國國家標準(C泣S) Α4規袼(210X297公i) 1293999 Δ Α7 _._Β7 五、發明説明（13) 其t實際上沒有流體對流發生。之後淤漿懸浮液可集中至 壓榨之濾心以大輻純化並乾可主要含貴金屬之於聚。 閱謂圖之敛述將更了解本發明。更特定地， 圖1 :為陶瓷膜濾心之透視圖； 圖2 :為根據本發明之電鍍工作件裝置之圖示。 圖1描述管1形式之陶瓷膜濾心。管由作為支撐3之高多孔 陶瓷材料製造，換言之，在本情況中為氧化鋁。在支撐3之 内侧有作為膜濾心層2之另一氧化物陶瓷層。該膜濾心層2 依次由一層（未明確顯示）組成，即由_ ai2〇3製造之第一 微過濾層及由Zr〇2及Ti〇2製造之第二微過濾層，Ti〇2之最 細孔大小使以如20,000道爾頓之排出孔大小過滤亦可行。 膜濾心層2之排出孔大小約20,000道爾頓。因此，平均孔大 小為約2 0奈米。 管之内直徑為約6毫米。管約1〇〇〇亳米高。壓力下流動以 編號4之方向進行。管之入口及出口間之壓力差範圍為15 至3巴。 為了收集通過管内壁之透過液，陶瓷管位在同中心之另 一管中。 圖2下半部包括二個圖1所示之過濾管1，過濾管1為具幾 個圖1所示形式之鑽孔的陶瓷管的部分。為了此目的1 9軸 鑽孔以例如由高度多孔陶瓷材料組成之陶瓷管中鑽孔，該 軸鑽孔為平行的。 在圖2之上半部中，部分顯示印刷電路板之加工裝置之加 工站。印刷電路板以加工方向R連績傳送通過不同之加工 80133-960119.doc ·16. ___ 本紙張尺度逋用中國國家樣準(C贷S) Α4規格(210X297公釐） 1293999 A7 ____— 〜_Β7 五、發明説明（14) 站。這樣方法之典型實例特別在WO 93/17153 A1中敘述。 在已執行預處理步驟後，印刷電路板（未顯示）在活化站 A-Pd浸入含膠態形式把之活化浴中。為了此目的，流體包 含在浸潰浴箱中。 之後，印刷電路板傳送通過三個連續之清洗站S i、s2及 s 3。這裏，附著在印刷電路板表面上之活化流體被連續清 洗掉。不同之清洗站Si、s2及S3提供喷頭作為此一目的。 清洗站Si、S2及S3以上開口之容器構成，其長邊之壁上安 排有噴頭。為了请洗掉附著之活化流體，清洗流體在印刷 電路板降低進入及/或升起離開清洗站Si、§2及83時喷灑在 電路板表面上。清洗流體分別在清洗站s i、s 2及s 3之容器 底部收集。新清洗流體以200升/小時之平均流速分配至清 洗站S 3 ’由此以與印刷電路板加工方向r相反之方向引導 至安排在其上游之清洗站S 2，由此在帶至清洗站s i，流速 維持相同，。每一清洗站s 1、s 2及S 3亦配置一收集箱（未顯 不）’其中分別收集清洗流體。收集之清洗流體在2〇〇升/小 時之流動速率由清洗站s i之收集箱排出進一步加工。 在印刷電路板表面藉清洗除去附著之活化流體後，其經 後處理。這樣之加工流體例如亞磺酸溶液。在後處理站B 中’印刷電路板浸入在處理容器中之這些溶液中處理。 之後，附著之後處理液再次在進一步之清洗站％、心及 S6.中清洗捧。同樣地，清洗流體由安排在清洗站、85及 S6中心喷頭噴灑在印刷電路板之表面上。收集之清洗流體 集中至收集箱（未顯示），由此以印刷電路板加工方向r相反 80133-960119.doc ” 本纸張尺度適財“雜準(CNS) A4規奶1()χ 2=爱)-—-- 1293999 A7 _______B7 五、發明説明（15 ) 之方向連續引導回安排在其上游之清洗站85及84。清洗流 f豆由凊洗站S 4排出，隨後至廢水處理。 其次印刷電路板浸入蝕刻站C-Pd中容器之蝕刻液中。這 裏’吸收至銅表面之鈀藉稍為蝕刻銅表面由活化移除。在 此情況中一樣，印刷電路板浸入蝕刻液中。 之後’附著之加工液再次由印刷電路板表面清洗掉。為 了此目的，印刷電路板傳送至清洗站S 7、S 8及S 9。附著在 印刷電路板表面之蝕刻液藉由喷頭喷灑在表面上之清洗流 體移除。為了此目的，新清洗流體在200升/小時之流速引 導至清洗站S9，在此清洗站收集之清洗流體收集在收集箱 (未顯示）中。同樣地，收集之清洗流體以與印刷電路板加 工方向R相反之方向由清洗站S9引導至清洗站％並由此進 入清洗站S?。由清洗站87，富鈀之清洗流體以2〇〇升/小時 之流速引導至再生裝置。 則面提，及之處理印刷電路板之方式只是一種可能之選 擇。印刷電路板亦可在稱為水平裝置中加工。由此電路板 以水平方向輸送且以水平或垂直之指向引導通過各站。在 不同之站中，流體藉喷頭輸送至表面。 由清洗站S4產生之清洗液實際上不含責金屬且可分配至 傳統廢水加工系統v比較上，由清洗站Si&S7產生之清洗 流體含有鈀且以本發明之方式再生·· 在第一個位置，種種清洗水分別收集在緩衝箱η ι及112 中。清洗流體由緩衝箱以2〇〇升/小時之流速排 出，其次分別由幫浦12.1及12·2引導至導管13」及13.2，並The method of the piece. The method of contacting the fluid with the workpiece is such as sprinkling, spraying, or cleaning fluid to the nozzle on the surface of the workpiece. This arrangement: or the release of the additive will reach the surface at high flow rates or when flow is required, such as when ΐ! In another embodiment of the invention, the contact is in a state in which the process fluid is discarded and the workpiece is immersed therein. The supporting method of the working piece can also be included in various forms. The working piece can be stored in a conventional manner such as a clamp, a screw clamp, a tong or a screw. In addition, the workpiece can be simply held, transported and handled in a horizontal position on a roll, wheel or cylinder or it can be sandwiched therebetween. In addition to the features previously mentioned, the apparatus also includes a means for separating at least one precious metal from the fluid. This facility includes at least one ceramic membrane having a discharge orifice size greater than 10,000 Daltons. The facility also includes a pump for transporting fluid to at least one membrane and directing fluid from contacting the workpiece to at least one of the ceramic membranes, the body conduit 0 pair of pumps, which refers to any non-motor operation or Refers to the simple transfer of fluid by gravity. According to the explanation provided above, there is a mixing facility for the separation of precious metals from fluids. In this mixing facility, the fluid from the point where the fluid contacts the workpiece can be mixed with the chemical. For this purpose, any conventional mixing facility known in the art of chemical reaction, such as a mixing plant and a mixing zone in a flow reactor, can be utilized. In addition, the facility for separating precious metals from fluids also has a multiphase separation unit' that can be deposited in a slurry where it is separated by fluid and from a facility where the precious metal is separated by the fluid. This form of multi-phase separation unit is formed by, for example, a settling box '80133-960119.doc _15_ This paper ruler ^Applicable to China National Standard (C Cr S) Α4 gauge (210X297 public i) 1293999 Δ Α7 _._Β7 V. Description of invention (13) Its t does not actually have fluid convection. The slurry suspension can then be concentrated to the press filter core to be extensively purified and dried to contain predominantly precious metals. The invention will be better understood by reference to the reference figures. More specifically, Figure 1: is a perspective view of a ceramic membrane filter; Figure 2: is an illustration of an electroplated workpiece device in accordance with the present invention. Figure 1 depicts a ceramic membrane filter in the form of a tube 1. The tube is made of a highly porous ceramic material as a support 3, in other words, alumina in the present case. On the inner side of the support 3 there is another oxide ceramic layer as the membrane filter layer 2. The membrane filter layer 2 is composed of one layer (not explicitly shown), that is, a first microfiltration layer made of _ai2〇3 and a second microfiltration layer made of Zr〇2 and Ti〇2, Ti〇2 The finest pore size allows filtration at a discharge orifice size of, for example, 20,000 Daltons. The membrane core 2 has a discharge orifice size of about 20,000 Daltons. Therefore, the average pore size is about 20 nm. The inner diameter of the tube is about 6 mm. The tube is about 1 metre high. The flow under pressure is in the direction of number 4. The pressure difference between the inlet and outlet of the tube ranges from 15 to 3 bar. In order to collect the permeate through the inner wall of the tube, the ceramic tube is positioned in the same tube in the same center. The lower half of Fig. 2 comprises two filter tubes 1 as shown in Fig. 1. The filter tubes 1 are part of a ceramic tube having several drilled holes in the form shown in Fig. 1. For this purpose, the 9-axis bore is drilled in a ceramic tube, for example consisting of a highly porous ceramic material, which is drilled in parallel. In the upper half of Fig. 2, a portion of the processing station of the processing unit of the printed circuit board is shown. The printed circuit board is conveyed in the processing direction R through different processing 80133-960119.doc ·16. ___ This paper scale is used in China National Standard (C loan S) Α4 specification (210X297 mm) 1293999 A7 ____—~_Β7 V. Description of invention (14) Station. A typical example of such a method is described in particular in WO 93/17153 A1. After the pre-treatment step has been performed, a printed circuit board (not shown) is immersed in the activation bath at the activation station A-Pd in a colloidal form. For this purpose, the fluid is contained in an impregnation bath. Thereafter, the printed circuit board is transported through three consecutive cleaning stations S i , s2 and s 3 . Here, the activating fluid attached to the surface of the printed circuit board is continuously cleaned off. Different cleaning stations Si, s2 and S3 provide nozzles for this purpose. A container for opening the openings Si, S2, and S3 is formed, and a nozzle is disposed on the wall of the long side. In order to wash away the attached activating fluid, the cleaning fluid is sprayed onto the surface of the board as the printed circuit board is lowered into and/or raised away from the cleaning station Si, § 2 and 83. The cleaning fluid is collected at the bottom of the vessel at the cleaning stations s i, s 2 and s 3 respectively. The fresh cleaning fluid is distributed to the cleaning station S 3 ' at an average flow rate of 200 liters per hour, thereby being directed in the opposite direction to the processing direction r of the printed circuit board to the cleaning station S 2 arranged upstream thereof, thereby being brought to the cleaning station Si, the flow rate remains the same. Each of the washing stations s 1, s 2 and S 3 is also provided with a collection tank (not shown) in which the cleaning fluid is separately collected. The flow rate of the collected cleaning fluid at 2 liters/hour is further processed by the collection tank of the cleaning station. After the attached activated fluid is removed by washing on the surface of the printed circuit board, it is post-treated. Such processing fluids are, for example, sulfinic acid solutions. In the post-treatment station B, the printed circuit board is immersed in these solutions in the processing vessel. Thereafter, after the attachment, the treatment liquid is again washed in the further cleaning station %, heart and S6. Similarly, the cleaning fluid is sprayed onto the surface of the printed circuit board by nozzles arranged at the cleaning station, 85 and S6. The collected cleaning fluid is concentrated to the collection box (not shown), so that the printed circuit board processing direction r is opposite 80133-960119.doc ” This paper scale is suitable for the fiscal (CNS) A4 regulation milk 1 () χ 2= Love)---- 1293999 A7 _______B7 V. The direction of the invention (15) continuously leads back to the cleaning stations 85 and 84 arranged upstream thereof. The purge stream f beans are discharged from the scrubbing station S 4 and subsequently to the wastewater treatment. Next, the printed circuit board is immersed in the etching solution of the container in the etching station C-Pd. Here, the palladium absorbed to the copper surface is removed by activation from a slightly etched copper surface. In this case as well, the printed circuit board is immersed in the etchant. The attached process fluid is then washed away again from the surface of the printed circuit board. For this purpose, the printed circuit board is transported to the cleaning stations S 7, S 8 and S 9. The etching liquid attached to the surface of the printed circuit board is removed by the cleaning fluid sprayed on the surface by the head. For this purpose, the fresh cleaning fluid is directed to the cleaning station S9 at a flow rate of 200 liters/hour, and the cleaning fluid collected at the cleaning station is collected in a collection tank (not shown). Similarly, the collected cleaning fluid is directed by the cleaning station S9 to the cleaning station % in the direction opposite to the printed circuit board processing direction R and thereby enters the cleaning station S?. From the cleaning station 87, the palladium-rich cleaning fluid is directed to the regeneration unit at a flow rate of 2 liters per hour. The way to handle printed circuit boards is just one possibility. Printed circuit boards can also be processed in what is known as a horizontal device. The board is thus transported horizontally and guided through the stations in a horizontal or vertical direction. In different stations, fluid is delivered to the surface by the nozzle. The cleaning liquid produced by the cleaning station S4 is practically free of metal and can be distributed to the conventional wastewater processing system v. The cleaning fluid produced by the cleaning station Si&S7 contains palladium and is regenerated in the manner of the present invention. At each location, various washing waters are collected in buffer tanks η and 112, respectively. The cleaning fluid is discharged from the buffer tank at a flow rate of 2 liters per hour, and secondly by the pumps 12.1 and 12.2 to the conduits 13" and 13.2, respectively.
A7 B7 1293999 五、發明説明（16) 輸送至共同導管13_3。為了調整pH，結合之清洗流體（若 需要）與pH調整劑（在本情沉中為NaOH)混合。為了此目 的，NaOH溶液由儲存槽丨4加入結合之清洗流體。電控電 路（未顯示）控制NaOH溶液之劑量。該控制電路包括pH探 針1 5 (例如pH測量電極）以控制NaOH溶液之計量幫浦。在 清洗流體之pH接近7之情況下，pH不需要調整到7之精確 值。 若利用離子或離子化鈀溶液取代鈀膠體液，其他適合化 學物質之溶液加入流體流動中取代pH調整劑確定含鈀流體 為可過滤的。 之後pH已調整至約7之值的清洗流體由另一 f浦12.3透 過導管13.4集中至收集箱16。 在收集箱1 6中有低液位感應器17.1及高液位感應器 17.2。右液位南於南液位感應器17.2 ’流體透過導管13.5 由容器16集中至幫浦18。比較上，若收集箱16之液位低於 低液位感應器17.1，清洗流體不由收集箱16打出。 藉幫浦18，流體在範圍為1.5至3巴之壓力下引導通過二 個串連之膜濾心管1。充滿管壁之透過流體排出至廢水處理 A。維持在過濾管之濃縮流體透過封閉之導管13.6循環， 故流體永久並持續對鈀濃縮。透過分枝13.7，部分濃縮清 洗流體永久回到收集箱16，由此藉幫浦18集中至膜濾心， 故鈀在此流體中呈梯度增加。 在收集箱1 6中，由濃縮產生之含鈀淤漿沉積在多粗分離 區中。該淤漿懸浮液可排出至另一容器1 9中。 _80133-960119.doc -19- 本紙張尺度適用中國國家標準(CfiS) A4規袼(210 X 297公釐) A7 B7 1293999 五、發明説明（17) 直接來自活化站A-Pd之流體亦可直接放出再生並集中至 超過濾。為了此目的，該流體可藉手使用編號Μ之路徑轉 移至收集箱20，或藉幫浦12.4將其小量引導至緩衝箱 11 · 1。已移除並藉手轉移至收集箱2 〇之流體之後可藉例如 另一幫浦12_5分配至收集箱16。 多相分離單元中容器16内之淤漿懸浮液集中至壓榨之遽 心2 1進一步分離鈀。壓榨之濾心2 1以虛線顯示在圖2中。 其含有孔大小為約5 0微米之濾心材料。壓榨之壓力為約4 巴。過濾流體可藉額外導管22循環回收集箱16或分配至潜 水處處理Α。 下面實例用於解釋本發明： 實例1 : 為進行試驗，印刷電路板以含400毫克/升之膠態鈀之膠 態、酸性活化流體，聚合物形式之保護膠體及次磷酸鋼形 式之還原劑處理。鈀膠體粒子之平均粒子直徑為約4奈米。 在清洗後，印刷電路板以含有機亞磺酸之後處理液處 理，之後再次清洗且最後在含300克/升之過硫酸鈉蝕刻液 中處理。藉此由銅表面移除鈀之量分配至蝕刻液，並透過 附著在印刷電路板表面之蝕刻液至隨後之清洗流體。 在前面提及之條件下在清洗站81至83及％至89(見圖2) 中得到之清洗流體分別分配至流速為200升/小時之所敛的 再生裝置。流體在陶瓷製造（α-Α12〇3作為支撐材料，有二 層Zr〇2及Ti〇2之超過濾層覆於其上，Ti〇2具最細之孔大小 且完成過濾之孔排出大小約20,000道爾頓；Ti〇2以凝膠法 80133-960119.doc -20· 本紙張尺度適用中國國家標準(C泣S) A4規格(210X297公釐) ^A7 B7 1293999 V. INSTRUCTIONS (16) Transport to the common conduit 13_3. To adjust the pH, the combined cleaning fluid (if needed) is mixed with a pH adjuster (NaOH in the sink). For this purpose, the NaOH solution is added to the combined cleaning fluid from storage tank 丨4. An electronically controlled circuit (not shown) controls the dose of the NaOH solution. The control circuit includes a pH probe 15 (e.g., a pH measuring electrode) to control the metering pump of the NaOH solution. In the case where the pH of the cleaning fluid is close to 7, the pH does not need to be adjusted to an accurate value of 7. If an ionic or ionized palladium solution is used in place of the palladium colloidal solution, other solutions suitable for the chemical are added to the fluid flow in place of the pH adjuster to determine that the palladium-containing fluid is filterable. The cleaning fluid whose pH has been adjusted to a value of about 7 is then concentrated by another pu 12.3 through the conduit 13.4 to the collection tank 16. In the collection box 16 there are a low level sensor 17.1 and a high level sensor 17.2. The right liquid level is located south of the South level sensor 17.2' fluid through conduit 13.5 from container 16 to pump 18. In comparison, if the level of the collection tank 16 is lower than the low level sensor 17.1, the cleaning fluid is not drawn by the collection tank 16. With the pump 18, the fluid is directed through two membrane filters 1 connected in series at a pressure ranging from 1.5 to 3 bar. The fluid passing through the wall is discharged to the wastewater treatment A. The concentrated fluid maintained in the filter tube is circulated through the closed conduit 13.6, so that the fluid is permanently and continuously concentrated on the palladium. Through branch 13.7, a portion of the concentrated cleaning fluid is permanently returned to the collection tank 16, whereby the pump 18 is concentrated to the membrane filter, so that the palladium increases in a gradient in the fluid. In the collection tank 16, a palladium-containing slurry produced by concentration is deposited in a plurality of coarse separation zones. The slurry suspension can be discharged to another container 19. _80133-960119.doc -19- This paper scale applies to Chinese National Standard (CfiS) A4 Specification (210 X 297 mm) A7 B7 1293999 V. Description of Invention (17) Fluid directly from the activation station A-Pd can also be directly Release regeneration and concentrate on ultrafiltration. For this purpose, the fluid can be transferred to the collection bin 20 by hand using the numbered path, or by a small amount to the buffer tank 11·1 by the pump 12.4. The fluid that has been removed and transferred to the collection bin 2 can be dispensed to the collection bin 16 by, for example, another pump 12_5. The slurry suspension in vessel 16 in the multiphase separation unit is concentrated to the core of the press 2 1 to further separate the palladium. The press filter 2 1 is shown in broken lines in Figure 2. It contains a filter material having a pore size of about 50 microns. The pressure of the press is about 4 bar. The filtered fluid can be circulated back to the collection tank 16 by additional conduits 22 or distributed to the sump to treat the helium. The following examples are intended to illustrate the invention: Example 1: For testing, a printed circuit board is a colloidal, 400 g/liter colloidal palladium, an acidic activating fluid, a polymeric form of protective colloid and a hypophosphorous acid in the form of a reducing agent. deal with. The palladium colloidal particles have an average particle diameter of about 4 nm. After cleaning, the printed circuit board was treated with an organic sulfinic acid-containing treatment liquid, then washed again and finally treated in a 300 g/liter sodium persulfate etching solution. Thereby, the amount of palladium removed from the copper surface is distributed to the etching liquid, and the etching liquid adhered to the surface of the printed circuit board is passed to the subsequent cleaning fluid. The cleaning fluids obtained in the cleaning stations 81 to 83 and % to 89 (see Fig. 2) under the conditions mentioned above were respectively distributed to the regenerative devices having a flow rate of 200 liters/hour. The fluid is made of ceramics (α-Α12〇3 as a supporting material, and two layers of Zr〇2 and Ti〇2 ultra-filter layers are coated thereon, Ti〇2 has the finest pore size and the size of the pores that complete the filtration is about 20,000 Daltons; Ti〇2 by gel method 80133-960119.doc -20· This paper scale applies to Chinese national standards (C weep S) A4 size (210X297 mm) ^
裝 A7 B7 1293999 五、發明説明（18) 塗佈）之濾心膜。清洗流體中鈀之濃度以及這些液體之pH 列在表1(試驗1及2)。 由清洗站81至83及87至S9產生之液體的pH未以pH調整 劑調整。 在超過濾時，濃縮流體以2,800升/小時之流速通過陶瓷 膜濾心處理。達到之透過流速為4 0至4 5升/小時。 在超過濾後，得到透過流體及濃縮流體。根據試驗1及2 之透過液及濃縮液中之飽濃度亦列在表1。 實例2 : 在另一試驗中，來自膠態活化流體及來自蝕刻液之清洗 流體混合物以1 : 1之體積比製備（試驗3 )。使用與實例1相 同之陶瓷膜濾心。結合清洗流體中最初抱濃度及混合物之 pH列於表1中。為了調整結合清洗流體之pH至7，加入 NaOH溶液至清洗流體中。 在進行超過濾後得到之透過液之鈀濃度<05毫克/升。濃 縮液中鈀濃度>1克/升（見表1)。 實例3 ： 在另一試驗4中，使用如實例1之相同陶瓷膜滤心。膠態 活化流體以1 : 1〇〇之體積比加入根據實例2得到之清洗流 體混合液中。此流體中鈀濃度等於15川毫克/升β此流體之 pH藉NaOH溶液調整至7。在進行超過滤後透過液及濃縮液 中鈀濃度列於表1中。 實例4 ： 在另一試驗5中，使用如實例1之相同陶瓷膜滤心。在此 80133-960119.doc _21_ 本紙張尺度適用中S S家標準(偷)A4規格(21GX297公釐) 晒~^ A7 B7 1293999 五、發明説明（19) 試驗中，使用無機活化劑溶液取代膠態活化液。活化劑含 有有機免錯合物（Neoganth® Activator，Atotech Deutschland GmbH ’德國），此溶液中鈀濃度為250毫克/升。 以此洛液活化之印刷電路板再次以二個清洗站S 1、S 2及 S 3之清洗階處理，清洗水之流動方向與圖2所示一致。清洗 站8〗產生之清洗水中鈀濃度為約1.5毫克/升。對調整清洗 水之超過濾能力，加入467克/升之二甲基二硫代胺基甲酸 鈉之水溶液至清洗水中。超過濾此溶液產生之透過液及濃 縮液中得到之鈀濃度列於表1(試驗5)。 實例5 ： 在另一試驗6中，使用如實例1之相同陶瓷膜濾心《在此 試驗中，根據實例4得到之清洗水以100 : 1之體積比例與 活化浴溶液混合。加入1 〇克/升之硫化鈉水溶液至混合物 中。最初鈀濃度為8.0毫克/升。在超過濾後濾液及濃縮液 中靶濃度,列於表1。 上面敘述之試驗產生具相當量淤漿之濃縮流體。在沉澱 淤漿後’濃縮液分配至壓榨之濾心。富鈀濃縮液之鈀濃度 為2至5克/升。在壓縮後得到濾餅的鈀濃度為2至15重量百 分比。 實例6 ： ^ 在另一試驗7中，使用如實例1之相同陶瓷膜濾心。根據 實例5之混合物以2 : 1之體積比加入根據實例2得到之清洗 流體的混合物。 此流體中鈀濃度為4.2毫克/升。pH藉NaOH溶液調整至 80133-960119.doc .22- 本紙張尺度適用中國國家標準(C校S) A4規袼(210X 297公釐） A7 B7 1293999 五、發明説明（20) 7。此外，加入467克/升之二甲基二硫代胺基甲酸鈉水溶液 至該流體中。在超過濾進行後透過液及濃縮液中鈀濃度列 於表1中。 應了解在此敘述之實例及具體實施例只作為描述之目的 及可見之種種修正與改變以及本申請案中敘述特徵之結合 將建議給熟諳此藝者且將包括在敘述本發明之精神及權限 内並在附帶申請專利範圍内。在此引用之所有公開案、專 利及專利申請案以提及之方式併入本文。 表1 : 試驗 編號 產物之混合物 最初 Pd 濃度 [mg/1] pH 透過液 中Pd 濃度 [mg/1] 濃縮液 中Pd 濃度 [mg/1] 添加化學藥品 1 清洗流體膠態活化劑 5.5 5 <0.5 >1，000 未添加 2 清洗流體蝕刻液 2.5 3 <0.5 >1，000 未添加 3 清洗流體膠態活化劑+蚀 刻液：1 : 1 4.0 7 <0.5 >15000 NaOH 4 清洗流體膠態活化劑+蝕 刻液：1 : 1+1%體積計之 膠態活化劑 15.0 7 <0.5 >15000 NaOH 5 清洗流體離子化活化劑 1.5 8 <0.5 >1,000 二甲基二硫代 胺基甲酸Na 6 清洗流體離子化活化劑 +1%體積計之離子化活化 劑 8.0 8 <0.5 >1，000 Na2S 7 (清洗流體離子化活化劑 +1%體積計之離子化活化 劑)+清洗流體膠態活化劑 +清洗液蝕刻液：1 : 1 : 1 4.2 7 <0.5 >1，000 NaOH二甲基 二硫代胺基甲 酸Na 80133-960119.doc -23- 本紙張尺度適用中國國家標準(Ci?S) A4規#(210X 297公釐) 1293999 A7 B7 五、發明説明（ 21 ) 數字表： 1 陶瓷膜濾心 2 陶瓷濾心層 3 高度多孔陶瓷支撐管 4 流動方向 10 印刷電路板乏加工裝置 11.1，11.2 緩衝箱 12.1-12.5 幫浦 13.1-13.7 導管 14 儲存槽 15 pH探針 16 收集箱 17.1 低液位感應器 17.2 高液位感應器 18 幫浦 19 容器 20 收集箱 2 1 壓榨之濾心 22 導管 A-Pd 活化站 ' B 後處理站 S 1 - S 9 清洗站 C-Pd 钱刻站 Μ 以手移除 80133-960119.doc -24 - 本紙張尺度適用中國國家標準(C泣S) A4規格(210X297公釐) A7 B7 1293999 五、發明説明（ 22 ) A 廢水處理 R 印刷電路板之加工方向 80133-960119.doc -25- 本紙張尺度適用中國國家標準(C泣S) A4規格(210X 297公釐)A7 B7 1293999 V. Invention (18) Coating). The concentration of palladium in the cleaning fluid and the pH of these liquids are listed in Table 1 (Runs 1 and 2). The pH of the liquid produced by the washing stations 81 to 83 and 87 to S9 was not adjusted with the pH adjuster. At the time of ultrafiltration, the concentrated fluid was treated through a ceramic membrane filter at a flow rate of 2,800 liter / hour. The permeation flow rate reached is 40 to 45 liters/hour. After ultrafiltration, a permeate fluid and a concentrated fluid are obtained. The saturated concentrations in the permeate and concentrate according to Tests 1 and 2 are also listed in Table 1. Example 2: In another test, a cleaning fluid mixture from a colloidal activating fluid and an etchant was prepared in a volume ratio of 1:1 (Test 3). The same ceramic membrane filter as in Example 1 was used. The initial concentrations in the combined cleaning fluid and the pH of the mixture are listed in Table 1. In order to adjust the pH of the combined cleaning fluid to 7, a NaOH solution is added to the cleaning fluid. The palladium concentration of the permeate obtained after ultrafiltration was <05 mg/liter. The palladium concentration in the concentrate was > 1 g/l (see Table 1). Example 3: In another experiment 4, the same ceramic membrane filter as in Example 1 was used. The colloidal activating fluid was added to the cleaning fluid mixture obtained according to Example 2 in a volume ratio of 1:1. The palladium concentration in this fluid is equal to 15 mg/L. The pH of this fluid is adjusted to 7 by NaOH solution. The palladium concentrations in the permeate and concentrate after superfiltration were listed in Table 1. Example 4: In another experiment 5, the same ceramic membrane filter as in Example 1 was used. Here 80133-960119.doc _21_ This paper scale applies SS standard (stealing) A4 specification (21GX297 mm) Sun ~^ A7 B7 1293999 V. Invention description (19) In the test, the inorganic activator solution is used instead of the colloidal state. Activation solution. The activator contains an organic error-free compound (Neoganth® Activator, Atotech Deutschland GmbH 'Germany) with a palladium concentration of 250 mg/l. The printed circuit board activated by the Lok solution is again treated by the cleaning steps of the two cleaning stations S1, S2 and S3, and the flow direction of the washing water is identical to that shown in Fig. 2. The cleaning station 8 produces a palladium concentration of about 1.5 mg/L in the wash water. To adjust the ultrafiltration capacity of the washing water, an aqueous solution of 467 g/liter of sodium dimethyldithiocarbamate was added to the washing water. The palladium concentrations obtained by ultrafiltration of the permeate and concentrate produced by this solution are shown in Table 1 (Test 5). Example 5: In another test 6, the same ceramic membrane core as in Example 1 was used. In this test, the washing water obtained according to Example 4 was mixed with the activation bath solution in a volume ratio of 100:1. Add 1 kg/L of aqueous sodium sulfide solution to the mixture. The initial palladium concentration was 8.0 mg/l. The target concentrations in the filtrate and concentrate after ultrafiltration are shown in Table 1. The test described above produces a concentrated fluid having a substantial amount of slurry. After the slurry is precipitated, the concentrate is dispensed to the press filter. The palladium-rich concentrate has a palladium concentration of 2 to 5 g/l. The palladium concentration of the filter cake obtained after compression is from 2 to 15% by weight. Example 6: ^ In another experiment 7, the same ceramic membrane filter as in Example 1 was used. A mixture of the cleaning fluid obtained according to Example 2 was added in a volume ratio of 2:1 according to the mixture of Example 5. The palladium concentration in this fluid was 4.2 mg/l. The pH is adjusted by NaOH solution to 80133-960119.doc .22- This paper scale applies to Chinese national standard (C school S) A4 gauge (210X 297 mm) A7 B7 1293999 V. Invention description (20) 7. Further, 467 g/liter of an aqueous solution of sodium dimethyldithiocarbamate was added to the fluid. The palladium concentrations in the permeate and concentrate after the ultrafiltration were carried out are shown in Table 1. It will be appreciated that the examples and specific examples described herein are for the purpose of description and description of the embodiments of the invention And within the scope of the attached patent. All publications, patents, and patent applications cited herein are hereby incorporated by reference. Table 1: Mixture of test number products Initial Pd concentration [mg/1] pH Pd concentration in permeate [mg/1] Pd concentration in concentrate [mg/1] Adding chemicals 1 Washing fluid colloidal activator 5.5 5 < ;0.5 >1,000 not added 2 cleaning fluid etchant 2.5 3 <0.5 >1,000 not added 3 cleaning fluid colloidal activator + etchant: 1 : 1 4.0 7 <0.5 > 15000 NaOH 4 Washing fluid colloidal activator + etchant: 1: 1 + 1% by volume of colloidal activator 15.0 7 < 0.5 > 15000 NaOH 5 Washing fluid ionization activator 1.5 8 < 0.5 > 1,000 dimethyl Dithiocarbamic acid Na 6 cleaning fluid ionization activator + 1% by volume ionizing activator 8.0 8 <0.5 > 1,000 Na2S 7 (cleaning fluid ionization activator + 1% by volume ion Activator) + cleaning fluid colloidal activator + cleaning solution etching solution: 1: 1 : 1 4.2 7 <0.5 > 1,000 NaOH dimethyldithiocarbamic acid Na 80133-960119.doc -23 - This paper scale applies to Chinese National Standard (Ci?S) A4 Regulation #(210X 297 mm) 1293999 A7 B7 V. Invention Description ( 21 ) Digital Table: 1 Ceramic membrane filter 2 Ceramic filter core 3 Highly porous ceramic support tube 4 Flow direction 10 Printed circuit board spent processing device 11.1, 11.2 Buffer tank 12.1-12.5 Pump 13.1-13.7 Catheter 14 Storage tank 15 pH probe 16 Collection box 17.1 Low level sensor 17.2 High level sensor 18 Pump 19 Container 20 Collection box 2 1 Pressed filter 22 Conduit A-Pd Activation station ' B Post-treatment station S 1 - S 9 Cleaning station C-Pd Money engraving station Μ Remove by hand 80133-960119.doc -24 - This paper size applies to Chinese national standards (C weep S) A4 size (210X297 mm) A7 B7 1293999 V. Invention description ( 22 ) A Wastewater treatment R Printed circuit board Machining direction 80133-960119.doc -25- This paper scale applies to Chinese national standard (C weep S) A4 size (210X 297 mm)