558550 五、發明說明（1) 【發明領域】 本發明係有關一種P C B製程及電鍍製程中產生之含 銅廢液之處理方法，特別是將該廢水之PH值控制在3以下 的範圍，以硫化鈉或硫氫化鈉為反應劑’且採用氧化還原 電位計來控•制加藥量。 【發明背景】 按，PCB製程及電鍍製程中，皆會產生含有銅之廢 水，目前業界對其處理方法有：鐵系或鋁系置換法、氫氧 化物沉澱法及硫化物沉澱法。其中： 鐵系或鋁系置換法，係加入鐵系（如：FeC13或Fe2(S04)3 等）或鋁系（如：氧化鋁或PAC等），加以置換後，再用 氫氧化納（N a 0 Η )將P Η值提高至9 · 0以上，再加重捕劑， 加凝集劑凝聚沈澱後去除，其缺點如下： a·此法會造成污泥大量增加，相對也增加污泥處理費 用。 b.加藥$無法自動控制，須靠經驗來判斷，而產生排放 水不合格率偏高。 c·污泥銅含量大幅降低，不利於銅資源回收。 d·產生許多氫氣，易引燃或氫爆，操作不安全。 e.處理過程發熱量極大，需大量之冷卻水。 氫氧化物沉殿法，係在廢液中加入氫氧化# (Na 將PH值提高至9. 〇以上沉澱，其缺點如下： a.加藥量無法自動控制，須靠經驗來判斷。 b ·需將P Η值控制在非登f m n r 列你非书小的摩巳圍（約9 · 5至1 〇 · 5 ) 〇558550 V. Description of the invention (1) [Field of the invention] The present invention relates to a method for treating copper-containing waste liquid generated in a PCB manufacturing process and an electroplating process. In particular, the pH value of the waste water is controlled to be below 3 in order to cure Sodium or sodium thiohydride is the reactant ', and a redox potentiometer is used to control and control the dosage. [Background of the Invention] According to the PCB manufacturing process and the electroplating process, waste water containing copper is generated. At present, the industry's treatment methods are: iron or aluminum replacement method, hydroxide precipitation method and sulfide precipitation method. Among them: Iron-based or aluminum-based replacement method, where iron-based (such as: FeC13 or Fe2 (S04) 3, etc.) or aluminum-based (such as: alumina or PAC, etc.) is added, and then replaced with sodium hydroxide (N a 0 Η) Increase the value of P 至 to above 9 · 0, then increase the trapping agent, add the coagulant and remove it after coagulation and precipitation. The disadvantages are as follows: a. This method will cause a large increase in sludge and relatively increase the cost of sludge treatment. . b. The dosing of $ can not be controlled automatically, it must be judged by experience, and the unqualified rate of discharged water is high. c. The copper content of sludge is greatly reduced, which is not conducive to the recovery of copper resources. d. It produces a lot of hydrogen, which is easy to ignite or explode, and is unsafe to operate. e. The heat generated during the process is extremely large and requires a large amount of cooling water. The hydroxide sinking method involves adding hydroxide # (Na to increase the pH value to above 9.0 to precipitate in the waste liquid. The disadvantages are as follows: a. The dosage can not be controlled automatically and it must be judged by experience. B · It is necessary to control the value of P to the non-book fmnr column of your non-book small Capricorn (about 9.5 to 10.5).
五、發明說明（2) t易受水中錯合物、有機質干擾， 電路板製程廢纟，含有非常多 &去除效果’印刷 標準’而產生排放水不合格率偏高：成’所以難以達排放 d.如再以離子樹脂吸附銅離子n 增加處理成本。 入重捕劑的方式，則 硫化物沈澱法，雖早就眾所， C B製程及電鍍製程中產生之人 知硫化物處理p …、^展出有效加樂控制方式 手门部-直 明人乃經過不斷測試研究，使二：j、，有總於此，本發 f P "製程及電鍍製程中 成為了罪的處 【發明概要】 玍之3銅廢液之方法。 為反應劑，去除：：：力:二廉價之硫化鈉或硫氫化鈉做 較為穩定，4:;:::率與形成的膠羽 低業者的環保費；：：)干擾，以降 B製程及電鍍制p + A瓜匕物沈澱法成為可靠的處理P C 本發中產生之含銅廢液之方法。 水中鐵離早X 2 一目的係將含銅廢液控制在PH3以下，使 金屬幾乎—入t '尤澱，降低污泥鐵含量，則污泥中所含之 本發：ϋ有利於銅回收。 藥控制器，传 #目的係採用氧化還原電位計，為線上加 確的加藥，加藥量得隨著廢水中銅含量變化，做有效明 為達上5不再以經驗值或採定量加藥。 程中產生上=目的，本發明提出一種P c Β製程及電鍍製 之含銅廢液之處理方法，係將該廢液之？11值控制 558550V. Description of the invention (2) t is susceptible to interference by water complexes and organic matter, the circuit board process is wasteful, contains a lot of & removal effect 'printing standard' and the discharge water failure rate is high: it is difficult to reach Emission d. If copper ion is adsorbed by ion resin, the treatment cost is increased. The method of adding recapture agent is the sulfide precipitation method. Although it has been known for a long time, it is known that sulfide treatment in the CB process and the electroplating process.…, ^ Exhibited an effective Jiale control method. Continuous testing and research, so that two: j, there is always this, this issue f P " process and electroplating process has become a crime [Summary of Invention] 玍 3 copper waste liquid method. As a reactant, remove ::: force: two cheap sodium sulfide or sodium sulfide do more stable, 4:; ::: rate and the formation of rubber plume low environmental protection fees for the industry ;: :) interference to reduce the B process and Electroplated p + A melamine precipitation method has become a reliable method for treating copper-containing waste liquid generated in the PC. The purpose of iron in the water is early X2. The purpose is to control the copper-containing waste liquid below PH3, so that the metal almost enters t'youdian, and the iron content of the sludge is reduced. The essential content of the sludge: ϋ is conducive to copper recovery . Drug controller, pass # purpose is to use a redox potentiometer to add the exact dosage on the line, the dosage should be changed with the copper content in the wastewater. medicine. In the process, the purpose of the invention is to provide a method for treating copper waste liquid containing P c B process and electroplating. 11 value control 558550
五、發明說明（3) 在3以下後，加入硫化納或硫氫化納為反應劑，採用氧化 還原電位計（0RP )來自動控制反應劑之加藥量，將電位 控制在20 OmV到-30 OmV之間，同時攪拌器之攪掉速率為 250rpm以上，再加混凝劑（polymer)沉澱，去除硫化銅 使排放水達到放流標準（3PPm)以不，且可免除混;'凝劑使 用，減少污泥量，提升污泥銅含量，有利污泥資源回收。 【圖式之簡單說明】 圖一顯示本發明之流程示意圖。 【發明詳細說明】 二、為詳細揭露本發明，以下舉一實施例配合圖式作詳細 =明。圖一顯不本發明之流程不意圖，含銅廢液含銅量由 〉辰度30?111至1〇〇〇〇??111均可適用於本發明，复台 π 丹巴栝以下步 =係酸化，p c Β製程及電鑛製程中產生之含銅廢液 進入第一反應池後將硫酸加入該含銅廢液中，同 控制器控制硫酸加入量，使ΡΗ值維持在3以下，主要9夂 ，螯合劑（EDTA)的鍵結強度，使硫根更容易從聲人^士降 中將銅搶出，並使在整個去除流程中不會有逆反應二: :廢液中所含螫合劑的鍵結強度非常強，則需射；值泛 更低’然後將該含銅廢液排入第二反應池；步驟: J在第二反應池中將廉價之硫化鈉或硫氫化鈉加二該 S銅廢液中，使銅離子變成硫化銅（CuS )，其化學 ^ 為· 干V. Description of the invention (3) After 3 or less, add sodium sulfide or sodium thiohydride as a reagent, and use a redox potentiometer (0RP) to automatically control the dosage of the reagent, and control the potential to 20 OmV to -30 Between OmV, at the same time, the stirring speed of the stirrer is above 250 rpm, and then a coagulant (polymer) is added to precipitate, and the copper sulfide is removed so that the discharged water reaches the discharge standard (3PPm). Reduce the amount of sludge, increase the copper content of the sludge, and facilitate the recovery of sludge resources. [Brief description of the drawings] FIG. 1 shows a schematic flowchart of the present invention. [Detailed description of the invention] 2. In order to disclose the present invention in detail, one embodiment is described in detail below with reference to the drawings. Figure 1 shows that the process of the present invention is not intended, and the copper content of the copper-containing waste liquid from> 30 ° C to 111 ° C to 111 ° C can be applied to the present invention. It is acidified. After the copper-containing waste liquid produced in the pc Β process and the electric mining process enters the first reaction tank, sulfuric acid is added to the copper-containing waste liquid, and the amount of sulfuric acid is controlled with the controller to maintain the pH value below 3, mainly 9 夂, the bonding strength of the chelating agent (EDTA) makes it easier for sulfur radicals to snatch out copper from the vocalist and reduce the reverse reaction in the whole removal process. 2 :: 螫 contained in waste liquid The bond strength of the mixture is very strong, you need to shoot; the value is lower, and then the copper-containing waste liquid is discharged into the second reaction tank; Step: J In the second reaction tank, add cheap sodium sulfide or sodium sulfide In this S copper waste liquid, copper ions are changed to copper sulfide (CuS), and its chemical ^ is · dry
CuC12 + Na2S -> CuS + NaClCuC12 + Na2S-> CuS + NaCl
558550 五、發明說明（4) 利用氧化還原電位計（0RP )將電位控制在2〇〇mV到558550 V. Description of the invention (4) Use a redox potentiometer (0RP) to control the potential to 200mV to
曰mV之間以自動控制硫化鈉或硫氫化鈉加入量，伟 ^ $旱 |^ 丨 // y|N 、-思考厝液中銅含量變化，做有效明確的加藥，而不 ::::或採定量加藥，且經實驗証明，p C B製程及電 7 = 甲產生之含銅廢液在PH3以下，氧化還原電位若控 之乂^ ’水中銅離子濃度皆在卜，以下。此時攪拌工器 ^ 4·速率為25〇rpm以上，因為p CB製程及電鍍製程中 护成Ϊί1!廢液中，銅離子平均含量為50〜100叩爪，所以 挫=非常少’而硫化物所形成粒子很細，ϋ由快速攪 含‘麼:5機ί :來產生較大粒子以利於沈殿’然後將該 ’、。液排入第三反應池；步驟30係加混凝劑，在第三反 ;池:^凝劑（P°lymer )加入該含銅廢液中以利沉 機u 為8〇rpm至i2〇rpm，增加其碰撞 池；步驟4〇係n，、係^將==液排入第四反應 降至2—至5〇rpr„，： = f 拌器之授拌速率 排入第五反應池；牛二：接觸面積，然後將該含銅廢液 出合翻、' τ，π，步驟50係沉澱，係在第五反應池中沉澱 該排放水放流。且因ίϋ”準（3pPm)以下，然後將 -r 因S銅廢液控制在PH3以下，使水中鐵 雕子不被沈殿，降彳H、p染人曰 科 乎士入暑钯，古d氐泥鐵3 $，則污泥中所含之金屬幾 十70全疋銅有利於銅回收。 綜上所述，本發明所媳 產生之含銅廢液之處=一fp c B製程及電鑛製程中 加藥控制器，使硫化物：：二：用氧化還原電位計為線上 物沈瓜法成為可靠的處理p C B製程Between mV, the amount of sodium sulfide or sodium sulfide is automatically controlled. Wei ^ $ || ^ 丨 // y | N,-Think about the change in the copper content in the mash, and do an effective and clear dosing without ::: : Or use quantitative dosing, and it has been experimentally proven that the p CB process and electricity 7 = the copper-containing waste liquid produced by A is below PH3, and if the redox potential is controlled, the concentration of copper ions in the water is all below. At this time, the stirrer ^ 4 · rate is above 25 rpm, because the average content of copper ions in the waste liquid is 50 ~ 100 talons in the p CB process and the electroplating process, so the drop = very little, and the vulcanization The particles formed by the object are very fine, and they are quickly mixed with '?: 5 机 ί: to produce larger particles in favor of Shen Dian', and then the ','. The liquid is discharged into the third reaction tank. Step 30 is to add a coagulant to the third reaction tank. A coagulant (P ° lymer) is added to the copper-containing waste liquid so that the settling machine u is 80 rpm to i2. rpm, increase its collision cell; step 40, n ,, and ^ will discharge == the liquid into the fourth reaction to 2 to 50rpr ,, = f the mixing rate of the mixer into the fifth reaction tank Niu II: contact the area, and then the copper-containing waste liquid is turned out, 'τ, π, step 50 is the precipitation, the discharge water is precipitated in the fifth reaction tank to release. And because the "ϋ" standard (3pPm) or less, Then control the -r copper waste liquid below PH3, so that the iron sculptures in the water are not affected by Shen Dian, and H and p are dyed. The contained tens of 70 full rhenium copper is conducive to copper recovery. To sum up, the copper-containing waste liquid produced by the present invention = a fp c B process and a dosing controller in the electric mining process, so that the sulfide: 2: Second, use the redox potentiometer to sink the seeds Method becomes a reliable process p CB process
第7頁 558550 五、發明說明（5) 及電鍍製程中產生之含銅廢液之方法，可減少污泥量，提 升污泥銅含量，有利污泥資源回收，故已符合專利法發明 之要件，爰依法具文申請之，謹請 貴審查委員詳予審 查，並祈早曰賜准專利，至感德便。 以上已將本發明作一詳細說明，惟以上所述者，當不 能限定本發明實施之範圍。對熟悉該項技藝之人士，當可 對其進行各種等效之變化例，惟其均應包括在本發明之精 神及範圍内。Page 7 558550 V. Description of the invention (5) and the copper-containing waste liquid method produced in the electroplating process can reduce the amount of sludge, increase the copper content of the sludge, and facilitate the recovery of sludge resources. Therefore, it has met the requirements of the invention of the Patent Law. If you apply in accordance with the law and have a written application, I would like to ask your reviewing committee to examine it in detail and pray that you will grant a quasi-patent as soon as possible. The present invention has been described in detail above, but the above should not limit the scope of implementation of the present invention. For those skilled in the art, various equivalent variations can be made, but they should all be included in the spirit and scope of the present invention.
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