A7 B7_ 五、發明説明（1 ) 本發明技術係以浸漬-電解方式再生鉛金屬之技術， 功能上係以溼式製程，模組式單元建立鉛回收技術以取代 傳統製程中較污染之部份。其應用不僅可以回收廢鉛酸電 池，尙可回收鉛灰、鉛渣等其他鉛廢料。 國內金屬資源再生工業，爲製造業者提供穩定之料 源，其經濟貢獻相當可觀。在金屬資源匮乏的臺灣，再生 鉛更是製造鉛酸電池之最主要的原料，可見其重要性。鉛 酸電池由於技術成熟，用料簡單，性能良好故廣泛地應用 於汽機車，船泊等，佔電池市場之絕大部份並逐年增加需 求量，故以廢鉛酸電池爲主的鉛廢料之再生工業益發重 要。 經濟部中央揉準局貝工消费合作社印装 (請先聞讀背面之注$項再填寫本頁) 傳統的鉛回收技術以火法冶煉爲其唯一途徑，習知之 火法冶煉流程主要係將收集之廢鉛酸電池先經粉碎後，利 用水洗方式將塑膠部份回收再利用，剩餘部份即送入粗煉 爐進行冶煉。在粗煉爐之高溫環境下（至少750°C以上）， 尙須借用還原劑如煤焦及鐵屑等，將廢料中之鉛化合物還 原爲金屬狀態之粗鉛，再進入精煉爐中，配製成鉛錠或鉛 合金產品。此製程之粗煉爐及精煉爐的排氣中含有高量之 硫酸鉛、氧化鉛、氧化砷等毒性固體微粒子，須以熱交換 機、袋濾器、靜電集塵器等防污設備過濾，收集而得之煙 灰，再送回粗煉爐處理。此一流程有下列之缺點： (6)由於送入粗煉爐中所含鉛泥之化學成份複雜，須在高 溫工作環境下反應，而造成環保處理成本高漲，以致 生產成本日益升高。 -3 - 本紙張尺度速用中國困家梯準（CNS ) A4規格（210X297公釐] 經濟部中央標準局貝工消费合作社印装 A7 £7_ 五、發明説明（2 ) (7) 生產之鉛產品，在品質與純度方面並不理想，僅能供 國內有限之運用，其附加經濟效益有限。 (8) 鉛再生製程中產生之大量煙塵與鉛蒸氣，在經由空氣 污染防治設備處理後產生之固體廢棄物，亦僅以循環 回爐方式處理，耗費大量操作費用，而回收效益卻有 限。 (9) 粗煉爐利用重油然燒加熱，溫度須達750°C以上，以 致產生大量之C02廢氣。在未來之國際<：02排放限量 條約下，此行業將更加難以生存。 吾人有鑑於此，乃致力硏究開發低污染之新技術，期 以經濟的鉛廢料回收製程取代傳統之火法冶煉，此濕式冶 煉技術不僅須達到工業減廢及高品質鉛之回收，更符合新 近之C02排放減量之機能，係本發明之目的。 相關的濕式鉛回收技術，在歐美地區有許多不同之專 利製程。各專利之棊本之單元以浸漬、電析等爲主，其中 各製程所用之浸漬液不盡相同，且多無純化之步驟，致使 中間產物純度較差，造成電析過程效率低。爲改善此缺點， 西班牙所發展之 Placid 流程（Diaz，G. and Andrews, D.， “Placid-A clean process for recycling lead from batteries’’， Jounal of Metals, 1996, pp. 29-31)引進換沉反應與離子交 換膜，且採用HC1之浸漬循環再生，可避免廢酸之產生 問題，但Placid製程採一單純循環系統，受限於僅能使 用單純成份之鉛糊（pastes)爲原料，若要處理其他複雜之 鉛廢料則相當困難。本發明雖與Placid製程引用相同之 -4 - 本紙張尺度逍用中國國家榇芈（CNS ) A4说格（210X297公釐） ---------,參------if (請先聞讀背面之注$項再填寫本頁) A7 B7 五、發明説明（3 ) 浸漬液再生觀念，但本發明進一步開發包含浸漬循環與電 析循環的雙循環系統，並輔以浸漬液再生，於是可避免浸 漬液被不當稀釋與非鉛金屬離子濃縮的問題，而滿足反應 條件遠較電析條件嚴苛的浸漬循環，也因此對不同原料適 用性較廣泛。本發明之從鉛酸電池回收鉛的新技術主要包 含下列四個部份： (a) 分選處理一廢鉛酸電池經碎解後，先後以重介分 選及篩選方式除去塑膠及橡膠等雜質加予回收利 用、並分成鉛泥及硬鉛部份，該硬鉛部份直接送 入精煉爐以較低成本製成鉛產品。 (b) 浸漬循環—先前處理的鉛泥部份，以HC1(3〜5N) 與NaCl(200〜250g/l)調配成之浸漬液，在高溫下 將鉛泥中鉛成份以離子或錯離子方式釋出，經冷 卻析出氯化鉛結晶，固液分離後母液持續循環浸 潰操作，.以降低浸漬成本 經濟部中央標準局貞工消费合作社印装 (請先閱讀背面之注項再填寫本頁) 裝- 訂 (C)浸漬液純化-浸漬液在經過反應後，除本身與酸 濃度降低外，將雜有硫酸根與其他非金屬雜質成 份之累積，故須以添加石灰除硫及以鉛置換較低 氧化電位之非鉛金屬，並輔以電析法去除氧化電 位較高之非鉛金屬金屬雜質等，於是將浸漬液純 化恢復其品質以供持續循環使用》 (d)電析循環-浸漬循環所得之氯化鉛先於調配槽中 與低濃度HC1之鹽水形成飽和電解液，再以循環 方式進入離子交換膜電析槽中之陰極區隔中。此 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） i A7 _B7_ 五、發明説明（4 ) 電析反應，在陰極部份係Pb2+離子以高純度棉鉛 型態析出，在陽極部份則是電解水產生氧氣。陽 極所產之H+離子將通過陽離子交換膜與陰極產生 之cr離子結合成富於鹽酸水溶液，並用於回補浸 漬液及/或調配槽，而形成封閉式流程。 較佳地，於前述本發明之鉛酸電池回收技術中該重介 分選係採用重液選礦機轉速爲lrpm，重液以磁鐵礦配製， 並以磁選機處理後，循環使用。 較佳地，於前述本發明之鉛酸電池回收技術中該篩選 係以40~60網目之篩網篩分而形成可通過篩之鉛泥部份， 及不能過篩之橡膠及硬鉛部份。 較佳地，於前述本發明之鉛酸電池回收技術中該浸漬 液被維持在介於〇至-2的pH値，及使浸漬液具有介於400 至800微伏之氧化電位範圍。 當前述本發明之鉛泥中含硬鉛顆粒時，可選擇性地於 該浸漬液加入微量（0-5%)之雙氧水（H202)或漂白水 (NaCIO)。 經濟部中央橾準局貝工消费合作社印製 (請先閱讀背面之注f項再填寫本頁) 於前述本發明之鉛酸電池回收技術中該浸漬液所含低 氧化電位非鉛金屬者，如銻、銅、砷等，可以電析循環所 得之純鉛來置換去除，所得之低氧化電位非鉛金屬可被送 入該精煉爐中來連同硬鉛部份製成合金鉛產品。 於前述本發明之鉛酸電池回收技術中該浸漬液所含高 氧化電位非鉛金屬者，如錫、鋅等，在以電析法分離出來 後可被送入該精煉爐中來連同硬鉛部份製成合金鉛產品。 -6 - 本纸張尺度適用中國國家標率（CNS ) A4洗格（210X297公釐） 經濟部中央標準局貝工消費合作社印装 A7 __B7_ _ 五、發明説明（5 ) 本發明之鉛回收技術亦可單獨應用於含有以上低及高 氧化電位非鉛金屬之主成份爲硫酸鉛（PbS04)之鉛泥、鉛 胥及煙灰。 相較於火法冶金在高溫下操作可能對於工作人員及環 境造成之負面影響，以濕法冶金方式在低溫與溶液中進行 金屬回收之操作，可大幅降低前述之缺點，因此濕法冶金 技術已逐漸受到業界之重視。以下茲舉一較佳實施例，並 佐以圖式，詳細說明之，俾具體揭露本發明之技術內容， 以供鈞局之審理。 請參閱圖一所示，圖一係本發明之鉛酸電池之回收新 技術之流程。廢鉛酸電池首先以切碎機al予以破碎，瀝 出之硫酸電解液可收集回收處理後出售。剩下之破碎的廢 鉛酸電池以重液選礦機a2浮選出塑膠等回收再利用，繼 而以一篩a3篩選出一可通過篩的鉛泥部份及不能過篩的 部份。不能過篩的部份以一重液選礦機a4分選成一橡膠 (可回收再利用）及粗粒硬鉛部份。該粗粒硬鉛被直接送入 精煉爐bl製成鉛產品，此操作可以節省還原劑及降低原 操作溫度，進而節省操作成本。過篩之鉛泥部份，如以下 表一所示，主要成份爲卩5804佔80〜90%，另含少量的金 屬鉛、PbO，及電木等雜質。 •7 - 本紙張尺度逍用中國國家梂準（CNS ) A4规格（210X297公釐） --- n n ϋ IL. — — — — — — τ (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央榡準局員工消費合作社印製 五、發明説明（6 ) 表一、各類鉛廢料樣品之成份分析 樣品 元素成份 化合物成份 煙灰 1.給，硫；2.鉢，錫，鍊，砷，銅 l.PbS04; 2.Zn(OH)2, Sn02 鉛泥 1.給，硫：2.銘，鲜，銅，錫，鍊 l.PbS04; 2.Pb, PbO, Sn02 鉛膏 1.船，硫；2,銅，粹 l.PbS04 註：1-主要：2-次要 於浸漬循環中，利用高濃度鹽酸（3〜5N)與鹽水（NaCl， 200〜250 g/1)調配成之浸漬液，以小於1 : 10之固液比， 於密閉之玻璃襯裡之不銹鋼反應槽cl內反應，浸漬溫度 約90±10°C，浸漬時間約在1-2小時範圍內。在浸漬過程 中，鉛泥中PbS04、PbO、硬鉛等鉛化合物成份轉變成Pb2 + 及PbCl广離子狀態存在浸漬液中。飽和浸漬液被送入一 結晶槽c2，並由高溫被降至室溫，Pb2 +將與C1·結合而以 卩1)(：12結晶析出，剩餘母液由管路c4再循環回該不銹鋼反 應槽cl當作該浸漬液使用，於是鉛泥中之鉛成份將全數 轉換成PbCl2結晶，僅剩餘少量殘渣。在浸漬液中的轉換 反應式如下：A7 B7_ V. Description of the invention (1) The technology of the present invention is a technology of regenerating lead metal by dipping-electrolysis. Functionally, it uses a wet process. The module unit establishes lead recovery technology to replace the more polluting part of the traditional process. . The application can not only recycle waste lead-acid batteries, but also lead waste such as lead ash and lead slag. The domestic metal resource recycling industry provides stable sources for manufacturers, and its economic contribution is considerable. In Taiwan, where metal resources are scarce, recycled lead is the most important raw material for the manufacture of lead-acid batteries, which shows its importance. Lead-acid batteries are widely used in automobiles, motorcycles, and moorings due to their mature technology, simple materials, and good performance. They account for the vast majority of the battery market and increase demand year by year. Therefore, waste lead-acid batteries are the main source of lead waste. The recycling industry is becoming increasingly important. Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the note “$” on the back, and then fill out this page). Traditional lead recycling technology uses fire smelting as its only way. The conventional fire smelting process mainly involves The collected waste lead-acid battery is first crushed, and the plastic part is recovered and reused by washing, and the remaining part is sent to the roughing furnace for smelting. In the high-temperature environment of the roughing furnace (at least 750 ° C or higher), it is necessary to use reducing agents such as coal coke and iron filings to reduce the lead compounds in the waste to crude lead in the metal state, and then enter the refining furnace. Made of lead ingots or lead alloy products. The exhaust gas of the roughing furnace and refining furnace in this process contains high levels of toxic solid particles such as lead sulfate, lead oxide, and arsenic oxide, which must be filtered and collected by anti-fouling equipment such as heat exchangers, bag filters, and electrostatic dust collectors. The soot obtained is sent back to the crude furnace for processing. This process has the following disadvantages: (6) Because the chemical composition of lead mud contained in the crude furnace is complicated, it must be reacted in a high-temperature working environment, which causes the environmental protection treatment cost to rise, resulting in increasing production costs. -3-This paper is a standard for the use of China ’s poor family ladder (CNS) A4 (210X297 mm) printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7 £ 7_ 5. Description of the invention (2) (7) Lead produced The product is not ideal in terms of quality and purity, and can only be used in limited domestic applications, and its additional economic benefits are limited. (8) A large amount of smoke and lead vapor generated in the lead regeneration process is generated after being processed by air pollution prevention equipment. Solid waste is only treated by recycling and recycling, which consumes a lot of operating costs, but the recovery benefits are limited. (9) The crude furnace uses heavy oil to burn and heat, and the temperature must reach above 750 ° C, so that a large amount of CO2 exhaust gas is generated. Under the future international <: 02 emission limit treaty, this industry will be more difficult to survive. In view of this, we are committed to researching and developing new technologies with low pollution, hoping to replace the traditional fire smelting with an economical lead waste recycling process. This wet smelting technology must not only achieve industrial waste reduction and recovery of high-quality lead, but also more in line with the recent C02 emission reduction function, which is the purpose of the present invention. Technology, there are many different patent processes in Europe and the United States. The unit of each patent is mainly impregnation, electrolysis, etc. The impregnating solution used in each process is different, and there are no purification steps, resulting in intermediate products. Poor purity results in low efficiency of the electrolysis process. To improve this disadvantage, the Placid process developed in Spain (Diaz, G. and Andrews, D., “Placid-A clean process for recycling lead from batteries '', Jounal of Metals, 1996, pp. 29-31) The introduction of the sinking reaction and ion exchange membrane, and the use of HC1 impregnation cycle regeneration can avoid the problem of waste acid. However, the Placid process adopts a simple circulation system, which is limited to only using pure ingredients. The lead pastes (pastes) are used as raw materials, and it is quite difficult to handle other complex lead waste. Although the present invention is the same as the Placid process, the reference is -4-This paper uses the Chinese National Standard (CNS) A4 standard (210X297) Mm) ---------, see ------ if (please read the note $ on the back before filling this page) A7 B7 V. Description of the invention (3) Concept of regeneration of impregnating solution, But the invention is further developed Double-cycle system with impregnation cycle and electrolysis cycle, supplemented by impregnation solution regeneration, so that the problems of improper dilution and non-lead metal ion concentration of the impregnation solution can be avoided, and the impregnation cycle meeting the reaction conditions is far more severe than the electrolysis conditions. Therefore, it has a wider applicability to different raw materials. The new technology for recovering lead from lead-acid batteries of the present invention mainly includes the following four parts: The sorting and screening method removes impurities such as plastic and rubber, recycles them, and separates them into lead mud and hard lead. The hard lead is directly sent to the refining furnace to produce lead products at a lower cost. (b) Dipping cycle—preliminarily treated lead mud, immersion solution prepared with HC1 (3 ~ 5N) and NaCl (200 ~ 250g / l), the lead component of lead mud is ionized or mis-ioned at high temperature. It is released by way of cooling, and the lead chloride crystals are precipitated after cooling. After the solid-liquid separation, the mother liquor is continuously circulated and immersed. In order to reduce the cost of immersion, printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Page) Installation-Order (C) Purification of impregnating solution-After the impregnating solution has undergone the reaction, in addition to reducing the concentration of itself and the acid, it will accumulate impurities containing sulfuric acid and other non-metallic impurities. Lead replaces non-lead metals with lower oxidation potential, and is supplemented by electrolysis to remove non-lead metal impurities with higher oxidation potential, etc., so the impregnating solution is purified to restore its quality for continuous cycle use "(d) Electrolysis cycle -The lead chloride obtained in the dipping cycle first forms a saturated electrolyte with the brine of low concentration HC1 in the preparation tank, and then enters the cathode compartment in the ion exchange membrane electrolysis tank in a circulating manner. This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) i A7 _B7_ V. Description of the invention (4) Electrolytic reaction, Pb2 + ions are precipitated in the cathode part in the form of high-purity cotton lead. The anode is electrolyzed to produce oxygen. The H + ions produced by the anode will be combined with cr ions generated by the cathode through the cation exchange membrane to form an aqueous solution rich in hydrochloric acid and used to replenish the immersion solution and / or the preparation tank to form a closed process. Preferably, in the aforementioned lead-acid battery recycling technology of the present invention, the heavy-medium sorting system uses a heavy-liquid concentrator with a rotation speed of 1 rpm, the heavy liquid is prepared with magnetite, and is processed with a magnetic separator before being recycled. Preferably, in the aforementioned lead-acid battery recycling technology of the present invention, the screening is performed by sieving a 40 to 60 mesh sieve to form a lead mud part that can pass through the sieve, and a rubber and hard lead part that cannot be sieved. . Preferably, in the lead-acid battery recycling technology of the present invention, the impregnating solution is maintained at a pH of between 0 and -2, and the impregnating solution has an oxidation potential range of 400 to 800 microvolts. When the lead sludge of the present invention contains hard lead particles, a small amount (0-5%) of hydrogen peroxide (H202) or bleach (NaCIO) may be added to the impregnating solution. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the note f on the back before filling this page) In the aforementioned lead-acid battery recycling technology of the present invention, the impregnating solution contains a low oxidation potential non-lead metal, Such as antimony, copper, arsenic, etc., can be replaced by pure lead obtained by electrolysis cycle, and the resulting low oxidation potential non-lead metal can be sent to the refining furnace to make alloy lead products together with hard lead. In the aforementioned lead-acid battery recycling technology of the present invention, those high-oxidation potential non-lead metals such as tin and zinc contained in the impregnating solution can be sent to the refining furnace together with hard lead after being separated by electrolysis. Partially made into alloy lead products. -6-This paper size is applicable to China National Standards (CNS) A4 Washing (210X297 mm) Printed on the A7 __B7_ _ by the Central Standards Bureau of the Ministry of Economic Affairs __B7_ _ 5. Description of the invention (5) The lead recycling technology of the present invention It can also be applied to lead mud, lead thorium and soot whose main component is the lead sulfate (PbS04) containing the above low and high oxidation potential non-lead metals. Compared with the negative impact that pyrometallurgical operation at high temperature may have on workers and the environment, the metallurgical recovery of metals in low temperature and solution by hydrometallurgy can greatly reduce the aforementioned disadvantages. Therefore, hydrometallurgical technology has been Gradually attracted the attention of the industry. The following is a preferred embodiment, accompanied by drawings, which will be described in detail. The technical content of the present invention is specifically disclosed for trial by the Bureau. Please refer to FIG. 1. FIG. 1 is a flow chart of the new recycling technology of the lead-acid battery of the present invention. The waste lead-acid battery is first crushed by a shredder al, and the leached sulfuric acid electrolyte can be collected for recycling and sold. The remaining crushed waste lead-acid batteries are recovered and reused by flotation of heavy liquid concentrator a2, and then a sieve a3 is used to screen out a portion of lead mud that can pass through the sieve and a portion that cannot pass through the sieve. The part that cannot be sieved is sorted into a rubber (recyclable) and coarse-grained hard lead part by a heavy liquid concentrator a4. The coarse-grained hard lead is directly sent to the refining furnace bl to make a lead product. This operation can save reducing agents and reduce the original operating temperature, thereby saving operating costs. The sieved lead mud, as shown in Table 1 below, contains 80 ~ 90% 卩 5804, and contains a small amount of impurities such as metal lead, PbO, and bakelite. • 7-The paper size is in accordance with China National Standards (CNS) A4 (210X297 mm) --- nn ϋ IL. — — — — — — Τ (Please read the notes on the back before filling this page) A7 B7 Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. 5. Description of the invention (6) Table 1. Composition analysis of various lead waste samples. Sample element composition. Compound composition. Soot 1. Give, sulfur; 2. Bowl, tin, chain, Arsenic, copper l. PbS04; 2. Zn (OH) 2, Sn02 lead mud 1. feed, sulfur: 2. Ming, fresh, copper, tin, chain l. PbS04; 2. Pb, PbO, Sn02 lead paste 1. Ship, sulfur; 2, copper, l.PbS04 Note: 1-Main: 2-Second in the immersion cycle, using high concentration hydrochloric acid (3 ~ 5N) and brine (NaCl, 200 ~ 250 g / 1) The impregnating solution is reacted in a closed glass-lined stainless steel reaction tank cl with a solid-liquid ratio of less than 1:10, and the impregnation temperature is about 90 ± 10 ° C, and the impregnation time is about 1-2 hours. During the immersion process, lead compounds such as PbS04, PbO, and hard lead in lead mud are transformed into Pb2 + and PbCl ions in the immersion solution. The saturated impregnating solution is sent to a crystallization tank c2, and is reduced from high temperature to room temperature. Pb2 + will be combined with C1 · to form 卩 1) (: 12 crystals are precipitated, and the remaining mother liquor is recycled back to the stainless steel reaction through the pipeline c4. The tank cl is used as the impregnating solution, so the lead components in the lead mud are fully converted into PbCl2 crystals, leaving only a small amount of residue. The conversion reaction formula in the impregnating solution is as follows:
PbS04 + 2NaCl -> PbCl2 + Na2S04 PbO + 2HC1 — PbCl2 + H20 Pb + Pb02 +4HC1 — 2PbCl2 + 2H20 由於PbCl2之飽和（平衡）溶解度極低，爲維持高效率 -8 - 本紙張尺度通用中國國家梂準（CNS ) A4規格（210X297公釐） 1ί.裝 訂 (請先Μ讀背面之注$項再填寫本頁) 經濟部中央標準局貝工消費合作社印褽 A7 _____B7_ 五、發明説明（7 ) 之浸潰效果，因此在該浸漬液中須以鹽酸將酸鹼度維在 -〇·5以下，並可輔以雙氧水（H202)或漂白劑（NaCIO)將浸 潰液氧化電位控制在400微伏以上，以利PbCl42·錯離子 狀態存在，來大幅增加浸漬效率。以上述表一中之鉛灰、 鉛泥、鉛膏爲試料各取100克，加以1000毫升之浸漬液（4N HC1及200 g NaCl)，在適溫（90±10°C)下反應1.5小時， 其間並取出飽和浸漬液加予降溫、·析出氯化鉛晶體，再循 環剩餘母液浸漬使用數次，其每次浸漬結果，如表二所示， 均具有相當令人滿意的鉛回收率。 表二、各類鉛廢料4 菜品之浸漬效果 樣品 浸漬溶解率 鉛回收率 煙灰 65 - 75 90 - 95 鉛泥 85-95 90-98 鉛膏 70-80 90-95 浸漬液在經過持續反應後，除本身之cr與酸濃度降 低外，尙有硫酸根與其他非鉛金屬成份之累積，將嚴重影 響浸漬效果及結晶品質，故須經由除硫、換沉及電析等程 序將浸漬液純化以維護其品質。當浸潰液在使用一或數次 後，可將結晶析出氯化鉛後的剩餘母液送入一除硫槽c5， 於其中添加石灰與該剩餘母液中的硫酸根反應，生成石膏 沉積再過濾去除，澄淸之液體再進入另一置換沉降槽c6, 於其中置入由下述電析循環所獲得之純鉛粉來換沈非鉛金 -9 - 本紙張尺度通用中國國家標準（CNS ) A4規格（2丨0X297公釐） ---------(^----_--.订 (請先鬩讀背面之注f項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（8 ) 靥雜質，如銻、銅、砷等之氧化電位能較低者，所得之低 氧化電位非鉛金靥淤泥可被送入該精煉爐bl中來連同硬 鉛部份製成合金鉛產品。經純化後之浸漬液c7則送返浸 漬反應槽中，進行下一批次（Batch)反應。如是多次再循 環後，被再循環的浸漬液中之其他無法由鉛換沈的非鉛金 屬，如錫、鋅等之氧化電位能較高者，將逐漸累積至相當 濃度，此時可藉由電析純化步驟c8加以一倂去除而進一 步純化被再循環的浸漬液C7’。以電析純化步驟c8去除的 氧化電位較高非鉛電析金屬可被送入該精煉爐bl中來連 同硬鉛部份製成合金鉛產品。進行電析純化步驟c8所需 間隔，則依料源成份及浸漬液再循環次數而定，以不影響 結晶純度（99.99%以上）爲依歸。其反應式分別如下： 除硫反應 S04_ + Ca(OH)2 CaS04 + 2 〇Η· 換沉純化Pb + M,2+— Pb2+ + M, Μ,:非鉛金屬 電析純化 2Men+ + nH20~> n/2 02 + Me + 2nH+ Me :金屬 於該結晶槽c2所結晶析出的氯化鉛，被移出並進行 一電析循環處理而以純鉛形式被回收。於電析循環中，如 圖二所示，PbCl2結晶先於一調配槽dl中與含低濃度鹽酸 (0.1N)之鹽水溶液（NaCl，200〜250g/l)形成適當的飽和電解 液。再以泵浦循環方式將該飽和電解液送入一陽離子交換 膜分隔之電析槽d2的陰極槽15內近底部處.，同時亦自陰 極槽15的近頂部處抽出一富於鹽酸的水溶液由管路d3送 -10 - 本紙張尺度適用中國國家橾準（CNS )八4規格（210 X 297公釐） 一 —^1· In n I— n^i ^^1 ϋ· n HI m V4 (請先M讀背面之注$項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 B7_ 五、發明説明（9 ) 回至該調配槽dl及/或至浸漬反應槽cl以補充該調配鹽 水溶液及/或浸漬液。在電析槽d2中，其陰極10電極採 用鉛板，陽極20電極採用鍍鈦銅板。在室溫及使用約1000 A/m1 2 3 4電流強度於該電析槽<12進行電析反應。此電析反應， 在陽極槽25內爲以0.1N Η3Β03水溶液爲電解液之水電解 反應，產生氧氣及H +離子。在陰極槽15內爲電解PbCl2， 產生Pb金靥及Cr離子。陰極10表面Pb2 +將以純鉛形態 析出，在陽極20表面則有氧氣氣泡產生。以定時方式將 陰極板10上析出之綿狀純鉛刮下或自然掉落而收集。另 陽極槽25內所產生的H +離子向陰極移動，透過該陽離子 交換膜30而於該陰極槽15內與Cl_結合形成該富於鹽酸 (HC1)的水溶液。上述電析反應如下： 陰極反應 PbCl2 + 2e· — Pb + 2C1· 陽極反應 H20，1/2 02 + 2H+ + 2e· ---------^裝------訂 (請先閱讀背面之注$項再填寫本頁) 1 總反應 PbCl2 + H20 -> Pb + 1/2 02 + 2HC1 本發明可以有下列數項優點： 2 設計浸漬液循環及電析循環爲兩獨立循環系統爲主， 並輔以浸漬液再生等處理，而架構出一循環封閉式鉛 再生流程，達到廢棄物減量及淸淨生產之目標。 3 以濕式處理單元爲架構，沒有毒性煙塵及鉛蒸汽之產 生之慮，保護操作人員之安全及減少污染肪治之成本。 4 所產PbCl2及鉛成份分析結果（表三）顯示，廢料中之鈴， -11 - 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐) '~~~ 經濟部中央梯準局貝工消費合作杜印製 A7 _B7 _ 五、發明説明（10 ) 超過95%均轉換成？1)(：12結晶析出，由電析所得鉛亦屬 電解級，純度達四九以上，符合內銷及外銷用途。 表三、製程產物卩1>(：12與鉛之純度分析 雜質 PbCl2 鉛 Sb⑴ ND(3) ND As⑴ ND ND Sn⑴ ND ND Zn⑴ 21 ND Cu(2) ND 6 (1) ASTM 標準：Sb + Sn<95 ppm (2) ASTM 標準：< 15 ppm (3) ND :未能測出 本發明技術係以一電解方式再生回收鉛金屬之技術， 純係以溼式製程、模組式單元理念，並建立鉛回收技術， 其用途不僅可以回收鉛灰、鉛渣、鉛泥外，另外尙可回收 其他鉛廢料。 圖示之簡單說明 圖一係本發明從廢鉛酸電池回收鉛新技術之流程。 圖二係顯示圖一流程中氯化鉛經由調配槽dl與具陽離 子交換膜分隔之電析槽d2處理回收的細部流程。 •12 - 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） ----------： '哀-----^--订----^---1 (請先閲读背面之注意事項存球寫本頁) 五、發明説明（11 ) 圖號說明 al...切碎機 bl...精煉爐 c4、d3...管路 c7 、 c7’_ dl...調配槽 10…陰極 25...陽極槽 A7 B7 a2、a4...重液選礦機 cl...浸漬液反應槽 c5...除硫槽 純化浸漬液 a3...篩 c2...結晶槽 c6...沉降槽 c8...電析純化 d2...陽離子交換膜分隔之電析槽 15.. .陰極槽 20...陽極 30.. .陽離子交換膜 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -13 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）PbS04 + 2NaCl-> PbCl2 + Na2S04 PbO + 2HC1 — PbCl2 + H20 Pb + Pb02 + 4HC1 — 2PbCl2 + 2H20 Due to the extremely low saturation (equilibrium) solubility of PbCl2, in order to maintain high efficiency -8-This paper is a standard in China. 梂Standard (CNS) A4 specification (210X297 mm) 1ί. Binding (please read the note on the back before filling in this page) Printed on the A7 ___B7_ by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The immersion effect, so the pH must be below -0.5 with hydrochloric acid, and the oxidation potential of the immersion solution can be controlled above 400 microvolts with hydrogen peroxide (H202) or bleach (NaCIO). The existence of PbCl42 · wrong ion state can greatly increase the impregnation efficiency. Take 100 grams of lead ash, lead mud, and lead paste in Table 1 above as samples, add 1000 ml of dipping solution (4N HC1 and 200 g NaCl), and react for 1.5 hours at a moderate temperature (90 ± 10 ° C) In the meantime, the saturated impregnation solution was taken out to cool and precipitate lead chloride crystals, and the remaining mother liquor was immersed for several times. The results of each impregnation, as shown in Table 2, have a fairly satisfactory lead recovery rate. Table 2. Various types of lead wastes 4 Dip effects of dishes Samples Dip dissolution rate Lead recovery rate Soot 65-75 90-95 Lead mud 85-95 90-98 Lead paste 70-80 90-95 After continuous reaction, In addition to the reduction of cr and acid concentration itself, the accumulation of sulfate and other non-lead metal components will seriously affect the impregnation effect and crystal quality. Therefore, the impregnation solution must be purified through procedures such as desulfurization, sedimentation and electrolysis. Maintain its quality. After the immersion solution is used one or more times, the remaining mother liquor after leaching out of lead chloride can be sent to a sulfur removal tank c5, and lime is added to react with the sulfate in the remaining mother liquor to generate gypsum deposits and then filtered. After removing, the clear liquid enters another replacement sedimentation tank c6, and the pure lead powder obtained by the following electrolysis cycle is placed in it to exchange non-lead gold-9-This paper standard is generally Chinese National Standard (CNS) A4 specifications (2 丨 0X297mm) --------- (^ ----_--. Order (Please read the note f on the back before filling this page) Printed by the Industrial and Consumer Cooperatives A7 B7 V. Description of the invention (8) Plutonium impurities, such as antimony, copper, arsenic, etc., have lower oxidation potential, and the resulting low oxidation potential non-lead gold plutonium sludge can be sent to the refining furnace b Zhonglai together with the hard lead part is made into alloy lead product. The purified impregnation solution c7 is returned to the impregnation reaction tank for the next batch reaction. If it is recycled for many times, it is impregnated by recycling. Other non-lead metals in the liquid that cannot be replaced by lead, such as tin and zinc, which have higher oxidation potentials, will gradually To a considerable concentration, at this time, the recirculated immersion solution C7 'can be further purified by removing it by electrolysis purification step c8. The electrolysis purification step c8 has a higher oxidation potential and can remove non-lead electrolysis metals. It is sent to the refining furnace bl to make alloy lead products together with the hard lead part. The interval required for performing electrolysis purification step c8 depends on the source ingredients and the number of times the immersion solution is recycled, so as not to affect the crystal purity (99.99 % Or more) is dependent. The reaction formulas are as follows: Desulfurization reaction S04_ + Ca (OH) 2 CaS04 + 2 〇Η · Pb + M, 2+-Pb2 + + M, MH, electrolysis of non-lead metals Purified 2Men + + nH20 ~> n / 2 02 + Me + 2nH + Me: The lead chloride crystallized from the crystallization tank c2 is removed and subjected to an electrolysis cycle treatment to be recovered as pure lead. In electrolysis During the cycle, as shown in Figure 2, the PbCl2 crystals first form a proper saturated electrolyte with a salt solution (NaCl, 200 ~ 250g / l) containing low-concentration hydrochloric acid (0.1N) in a mixing tank dl before being pumped. The saturated electrolyte is sent to the cathode of an electrolysis cell d2 separated by a cation exchange membrane in a cyclic manner. Near the bottom of the tank 15. At the same time, an aqueous solution rich in hydrochloric acid is also drawn from the near top of the cathode tank 15 and sent to the pipeline d3 -10-This paper size is applicable to China National Standard (CNS) 8-4 (210 X 297 mm) One — ^ 1 · In n I— n ^ i ^^ 1 ϋ · n HI m V4 (Please read the note on the back before filling in this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation A7 B7_ V. Description of the invention (9) Return to the preparation tank dl and / or to the immersion reaction tank cl to supplement the preparation saline solution and / or immersion solution. In the electrolytic cell d2, the cathode 10 electrode is a lead plate, and the anode 20 electrode is a titanium-plated copper plate. The electrolysis reaction was carried out at room temperature under a current intensity of about 1000 A / m1 2 3 4 in this electrolysis cell < 12. This electrolysis reaction, in the anode cell 25, is a water electrolysis reaction using a 0.1N Η3B03 aqueous solution as an electrolytic solution to generate oxygen and H + ions. PbCl2 is electrolyzed in the cathode tank 15 to generate Pb Au and Cr ions. On the surface of the cathode 10, Pb2 + will be precipitated as pure lead, and on the surface of the anode 20, oxygen bubbles will be generated. The cotton-like pure lead precipitated on the cathode plate 10 was scraped off or dropped naturally in a timed manner and collected. In addition, the H + ions generated in the anode tank 25 move to the cathode, pass through the cation exchange membrane 30 and combine with Cl_ in the cathode tank 15 to form the aqueous solution rich in hydrochloric acid (HC1). The above electrolysis reaction is as follows: Cathode reaction PbCl2 + 2e · — Pb + 2C1 · Anode reaction H20, 1/2 02 + 2H + + 2e · --------- ^ 装 ------ Order (please Read the note on the back of the page before filling in this page) 1 Total reaction PbCl2 + H20-> Pb + 1/2 02 + 2HC1 The invention can have the following advantages: 2 The design of the impregnating solution cycle and the electrolysis cycle are two independent The circulation system is mainly supplemented by treatments such as impregnating solution regeneration, and a closed loop lead regeneration process is constructed to achieve the goals of waste reduction and net production. 3 Based on a wet processing unit, there is no concern about the generation of toxic smoke and lead vapor, which protects the safety of operators and reduces the cost of pollution treatment. 4 The analysis results of the produced PbCl2 and lead (Table 3) show that the bell in the waste, -11-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) '~~~ Central Ladder Bureau of the Ministry of Economic Affairs Shelley Consumer Cooperation Du printed A7 _B7 _ 5. Description of invention (10) More than 95% are converted into? 1) (: 12 crystals are precipitated, and the lead obtained by electrolysis is also electrolytic grade, with purity of more than 49, which is suitable for domestic and foreign use. Table III. Process products 卩 1 > (: 12 and lead purity analysis impurity PbCl2 lead Sb⑴ ND (3) ND As⑴ ND ND Sn⑴ ND ND Zn⑴ 21 ND Cu (2) ND 6 (1) ASTM standard: Sb + Sn < 95 ppm (2) ASTM standard: < 15 ppm (3) ND: not measured The technology of the present invention is a technology that regenerates lead metal by an electrolytic method. It is purely based on the wet process and modular unit concept, and establishes lead recovery technology. Its use can not only recover lead ash, lead slag, lead mud, In addition, other lead waste materials can be recovered. The simple illustration of the figure is a process of the new technology for recovering lead from waste lead-acid batteries according to the present invention. Detailed process of separation and recovery of separated electrolyzer d2. • 12-This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ----------: 'wai ---- -^-Order ---- ^ --- 1 (Please read the notes on the back to write this page first) 5. Description of the invention ( 11) Drawing number description al ... shredder bl ... refining furnace c4, d3 ... pipes c7, c7'_dl ... dispatching tank 10 ... cathode 25 ... anode tank A7 B7 a2 a4 ... heavy liquid concentrator cl ... impregnation liquid reaction tank c5 ... sulfurization tank purification impregnation liquid a3 ... sieve c2 ... crystallization tank c6 ... settling tank c8 ... electrolytic purification d2 ... electrolysis cell separated by cation exchange membrane 15 ... cathode cell 20 ... anode 30 ... cation exchange membrane (please read the precautions on the back before filling this page) Printed by Consumer Cooperatives-13 This paper size applies to China National Standard (CNS) A4 (210X297 mm)