201119946 六、發明說明： 【發明所屬之技術領域】 本案係關於一種由類似廢電池或鉛礦之回收電極漿料黏液等 含雜質混合物再生高純度錯化合物之技術。 【先前技術】 以申請人名義，且其内容已藉明確參考方式併入本案中之先 前PCT專利申請案第PCT/IT2008/0_22號，係不同於以鍛燒為 基礎而由廢棄鉛電池或鉛礦回收電極漿料再生有價值鉛内各物之 長期建立製程，而㈣-種賴方法，其解完全根據回二電極 漿料或錯礦之濕式處理法絲礎，能_大量減少處理有害殘留 物之負擔及有效之試做用，以高產率製造高度純化之碳 然而’為使用再生财製作新電池㈣，必須藉加熱碳酸^大 約400至450°C，以將碳酸鉛分解成氧化鉛。這就所需能量而士， 係屬非常昂貴者。 、、依據上述先前PCT專财請案所揭露之方法，呈電極聚料黏 硬或呈經細磨且最終預處理鉛礦形式之起始材料，係藉使用不同 於硫酸酸’並加人可針對存在於該起始材料中之二氧化錯使 過氧化氫或其他還糊、及可將所有純合物皆轉化成不可 ^硫酸鉛之硫酸，以達成賴，該硫酸純相其他不可溶物質 一同分離，且之後選擇性地溶解於一可溶解化合物之一水溶液 中。將-碳酸鹽加至經分離之透明硫酸麟液，以沉搬出碳酸 碳酸船。 、除最終將碳酸鹽轉化成氧化船所需之能量外，該含雜質起始 材料之酸麵錢賴包含某些蚊成本及處置設備之複雜性 201119946 【發明内容】 為降低錯再生於處理容器及相關攪拌器、加熱器及/或冷卻 器、過滤器、總體處理設備之複雜性、泵送及能量需求等設備財 產方面之成本，申請人已發現，將全濕式鉛再生製程流作極為有 效之簡化，不僅可行，甚至更有效率。 已意外地發現，極為有效之新穎方式在於，直接將含雜質起 始材料懸浮於一醋酸鹽之一硫酸鉛溶解水溶液中，且將過氧化氫 或一亞硫酸鹽加入其中，或可依選擇地將一亞硫酸酐起泡通過其 中’以其一適合劑量將預期存在於該含雜質起始材料中之任何二 氧化鉛還原成氧化鉛，並以一適合劑量之硫酸將所有氧化鉛轉化 成酸鉛’其仍保持溶解於所選之溶解鹽溶液中。 接著可使一内含該溶解硫酸鉛之一透明溶液，與包含該含雜 質起始材料中之所有未溶解雜質之一固相殘留物相分離。 例如次硫酸鹽或其他氧化物等不溶於該醋酸鹽溶液中之某些 疋在〇化0物可能存在’其取決於待處理之含雜質起始材料原始 物，將伴隨該硫酸鉛溶解醋酸鹽溶液分離出之所有固相不可溶物 =’―同存在。此未由該醋酸鹽溶液溶解之化合物中之鉛，若考 量、左濟性或基於其他必須如此之理由時’最終可加以再生。其可 藉由將雜質及不可溶鉛化合物所構成之經分離固相物質，懸浮於 與醋酸鹽具相同陽離子之氫氧化物之—濃縮溶液中以進行分解， 且將該等化合物轉化成可溶解亞鉛酸鹽來實施，該等可溶解亞鉛 酸鹽係可轉於錢氧化物溶液中，接著可使縣液與仍不可^ =質相分離。將現含有自先前分離出之固相雜質中汽提出之殘留 鉛又氫氧化物溶液，加入容器内含硫酸鉛之液體醋酸溶液中，其 =可加入該與醋酸鹽具相同陽離子之氫氧化物，以將該液體醋酸 、、液中所含呈硫酸錯形式之錯，依氧化或氫氧化鉛形成沉殿。 201119946 接著’可藉由如先前PCT專利申請案第PCT/IT2008/000022 號揭露方法所考慮者，將用於選擇性溶解硫酸鉛之與醋酸鹽具相 同1%離子之碳酸鹽加至該溶液中，以使不可溶之碳酸/次碳酸船沉 澱，或更佳地依據一變型具體實施例，以用於選擇性溶解硫酸鉛 之與醋酸鹽具相同陽離子之氫氧化物取代一碳酸鹽，加至透明硫 酸鉛溶液中，而依據沉澱浴之溫度，造成鉛氧化物或氫氧化物沉 澱，以達成由透明硫酸鉛溶液沉澱高純度鉛化合物，如此甚至可 免除最終必須藉於一烘箱中加熱碳酸鹽而將再生碳酸鉛轉化成氧 化鉛之負擔。 申請人已發現，不論使用一碳酸鹽或一氫氧化物來造成沉 澱，實際上皆可完成賴溶液中之所有m殿為高純度之錯化 〇物。因此，可由該含雜質起始材料已懸浮於其中之相同醋酸溶 液，實施一固相高純度鉛化合物與該醋酸溶液之分離。 儘管該透明醋酸鹽溶液逐漸變得富含有用於選擇性地溶解硫 酸鉛之與醋酸鹽具相同陽離子之硫酸鹽，然其可再循環至該含雜 質起始材料懸浮步驟，只要硫酸納濃度⑽持於飽和以下即可。 當該透明醋酸鹽溶液中之硫酸鹽濃度趨近飽和時，可將該溶液冷 卻至大約lGt，以選擇性地使所使用醋酸鹽之陽離子硫酸鹽组^ 之固相物質結晶及㈣，而可藉由·來回收。接著可將益硫酸 鹽之透明酷酸鹽溶液，再循環至該含雜f起始材料之懸浮浴。 較佳地，於將該雜冷卻，以選擇性地使所使用醋酸鹽之陽 離予硫酸脸成之關物質結晶及沉料，經輯充有勢合樹脂 〈-分離柱來賴鋪酸溶液，以於冷卻絲社㈣該溶液中 之任何殘_離子進行分離，以產生具有較廣 鉛硫酸鹽副甚物。 … 201119946 【實施方式】 實施例1 請參考圖一之流程圖，依據本發明方法之一第一具體實施 例，其為特別適合於處理回收自壓碎廢棄電池之原始電極漿料黏 液，但藉最終繁瑣調適，而亦可用於細磨船礦，如通常經焙燒以 將亞&酸氣轉化成硫酸鉛之方船礦、硫酸鉛礦及較不普遍礦物 等，其中含雜質起始固體材料係懸浮於，能溶解硫酸鉛之例如一 鈉，銨，鉀，脲，單、二或三乙醇胺醋酸鹽於一鹽類水溶液中。 為達成此懸浮，以可滿足將所有存在於該起始材料中之氧化 物皆轉化成硫酸鹽之適合劑量硫酸，及選自過氧化氫、一亞硫酸 鹽及亞硫酸酐之一適合劑量還原劑，係逐步加至或經起泡而通過 該懸浮浴，達可滿足將内含於該起始材料中之任何二氧化鉛(來自 拋棄錯電池之黏液係如此）皆還原成氧化錯。 因此，於圖一製程流程圖之第一步驟(1)中，該起始材料之懸 浮浴將發生數個化學反應，以下係基於該等反應係同步發生，使 所有鉛化合物皆轉化成硫酸鹽，其可溶解於内含有上述特定溶解 鹽之水溶液中。 由以下所述之反應，可清楚認知存在有一協同性作用，其可 導致化學轉化製程之速度明顯增加，此係基於硫酸鉛溶解將釋 放，其於電極_中原本緊密結合之氧化鉛(針對廢棄料池電極 漿料黏液之情況），以形成3Pb0PbS04及4Pb0PbS04類型之化合 物，使氧化物快速反應，將其本身轉換成硫酸鹽，該硫酸鹽接^ 又溶解於，於此所考量具體實施例中為醋酸鈉之醋酸鹽溶液中， 且同時，物理性嵌入以上所指次硫酸鹽結核中之二氧化鉛，變得 可由反應物更輕易地觸及且更快速地還原成氧化鉛。 以下反應係關於由廢棄鉛電池之電極聚料黏液再生高純度鉛 201119946 化合物之一範例具體實施例’其中硫酸船係呈含雜質起始材料中 之測量成分(接近大約重量百分率60%)且溶解於醋酸鈉水溶液中。 反應1:溶解硫酸鉛201119946 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a technique for regenerating a high-purity compound by an impurity-containing mixture such as a waste battery or lead ore recovered electrode slurry. [Prior Art] In the name of the applicant, and its contents have been incorporated into the prior PCT Patent Application No. PCT/IT2008/0_22 by way of a clear reference, which is different from the lead-based battery or lead based on calcination. The mineral recovery electrode slurry regenerates the long-term establishment process of valuable materials in lead, and (4)-the method of seeding, the solution is completely based on the wet treatment method of the second electrode slurry or the wrong mineral, which can reduce the harmful treatment Residue burden and effective trial use, high-purity carbon is produced in high yield. However, to make a new battery (4) for use in renewables, it is necessary to heat the carbonate to about 400 to 450 ° C to decompose lead carbonate into lead oxide. . This requires energy and is very expensive. According to the method disclosed in the previous PCT special wealth application, the starting material of the electrode material is hard or finely ground and finally pretreated in the form of lead ore, which is different from sulfuric acid. For the dioxins present in the starting material, hydrogen peroxide or other paste, and all the pure compounds can be converted into sulfuric acid which cannot be lead sulfate, to achieve the pure insoluble other substances. They are separated together and then selectively dissolved in an aqueous solution of one of the soluble compounds. The carbonate was added to the separated clear sulfuric acid sulphate to carry out the carbonic acid carbonate ship. In addition to the energy required to ultimately convert the carbonate into an oxidizing vessel, the acidity of the impurity-containing starting material includes some mosquito costs and the complexity of the disposal equipment. 201119946 [Summary of the Invention] And the costs associated with equipment such as mixers, heaters and/or coolers, filters, overall processing equipment complexity, pumping and energy requirements, the Applicant has found that the full wet lead regeneration process is extremely Effective simplification is not only feasible but even more efficient. Surprisingly, it has been found that the most effective novel method is to directly suspend the impurity-containing starting material in an aqueous solution of lead sulfate dissolved in one of the acetic acid salts, and add hydrogen peroxide or a sulfite thereto, or alternatively The sulfite anhydride is bubbled through to reduce any lead dioxide that is expected to be present in the impurity-containing starting material to lead oxide at a suitable dose thereof, and convert all lead oxide to acid with a suitable amount of sulfuric acid. Lead's remain dissolved in the selected dissolved salt solution. A clear solution containing one of the dissolved lead sulfates can then be separated from the solid phase residue comprising one of all undissolved impurities in the impurity-containing starting material. For example, some cesium salts or other oxides that are insoluble in the acetate solution may be present in the bismuth oxide. 'It depends on the original material of the impurity-containing starting material to be treated, and will dissolve the acetate with the lead sulfate. All solid phase insolubles separated by the solution = '- coexist. The lead in the compound which is not dissolved by the acetate solution can be regenerated if it is considered, left-handed or otherwise necessary for such reasons. It can be decomposed by dissolving the separated solid phase material composed of impurities and insoluble lead compounds in a concentrated solution of a hydroxide having the same cation as the acetate, and converting the compounds into a soluble one. The lead acid salt is used to carry out, and the soluble lead salts can be transferred to the money oxide solution, and then the county liquid can be separated from the qualitative phase. The residual lead and hydroxide solution which is stripped from the previously separated solid phase impurities is added to the liquid acetic acid solution containing lead sulfate in the container, which can be added to the hydroxide having the same cation as the acetate In order to form the sinking chamber according to oxidation or lead hydroxide, the liquid acetic acid and the liquid are in the form of a wrong form of sulfuric acid. 201119946 The following is a method of selectively dissolving lead sulfate with the same 1% ion of acetate as the acetic acid salt, as considered in the method disclosed in the PCT Patent Application No. PCT/IT2008/000022, to the solution. To precipitate an insoluble carbonate/carbonic acid ship, or more preferably according to a variant embodiment, to replace the monocarbonate with a hydroxide having the same cation as the acetate salt for selectively dissolving lead sulfate, In a transparent lead sulfate solution, depending on the temperature of the precipitation bath, lead oxide or hydroxide precipitates to achieve high-purity lead compounds precipitated from a transparent lead sulfate solution, so that even the final need to heat the carbonate in an oven And the burden of converting recycled lead carbonate into lead oxide. Applicants have discovered that, regardless of the use of a monocarbonate or a hydroxide to cause precipitation, virtually all of the m-thinks in the solution are highly pure, staggered. Therefore, separation of a solid phase high-purity lead compound from the acetic acid solution can be carried out by the same acetic acid solution in which the impurity-containing starting material has been suspended. Although the transparent acetate solution gradually becomes rich in sulfate having the same cation as the acetate for selectively dissolving lead sulfate, it can be recycled to the impurity-containing starting material suspension step as long as the sodium sulfate concentration (10) Hold below saturation. When the concentration of the sulfate in the transparent acetate solution approaches saturation, the solution may be cooled to about 1 Gt to selectively crystallize the solid phase material of the cationic sulfate group of the acetate used and (4). Recycle by ·. The clear sulfate solution of the sulphate can then be recycled to the suspension bath containing the starting material. Preferably, the impurities are cooled to selectively oxidize the cation of the used acetate to the surface of the sulfuric acid, and the material is crystallized and condensed, and the mixture is filled with a potential resin. In order to separate any residual ions in the solution (4) to produce a relatively broad lead sulfate by-product. [2011] [Embodiment] Embodiment 1 Referring to the flowchart of FIG. 1, according to a first embodiment of the method of the present invention, it is particularly suitable for processing the original electrode slurry mucilage recovered from the crushed waste battery, but borrowing In the end, it can be used for fine grinding, and it can also be used for fine grinding of ship ore, such as Fangfang mine, lead sulfate ore and less common minerals, which are usually calcined to convert Ya & acid gas into lead sulfate, which contains impurities and starting solid materials. Suspended in, can dissolve lead sulfate such as monosodium, ammonium, potassium, urea, mono-, di- or triethanolamine acetate in a salt aqueous solution. To achieve this suspension, a suitable dose of sulfuric acid which satisfies all of the oxides present in the starting material into sulfates, and one selected from the group consisting of hydrogen peroxide, monosulfite and sulphuric acid is suitable for dose reduction. The agent is gradually added to or foamed through the suspension bath to satisfy any reduction of lead dioxide (such as the mucus from the discarded battery) contained in the starting material to oxidative error. Therefore, in the first step (1) of the process flow chart of Figure 1, a plurality of chemical reactions will occur in the suspension bath of the starting material, and the following steps are based on the simultaneous reaction of the reaction systems to convert all lead compounds into sulfates. It can be dissolved in an aqueous solution containing the above specific dissolved salt. From the reaction described below, it is clear that there is a synergistic effect, which can lead to a significant increase in the speed of the chemical conversion process, which is based on the dissolution of lead sulfate, which is originally tightly bound to the lead in the electrode (for waste In the case of the cell electrode slurry mucilage, to form a compound of the type 3Pb0PbS04 and 4Pb0PbS04, the oxide is rapidly reacted, and the oxide itself is converted into a sulfate, which is dissolved in the specific embodiment. In the acetate solution of sodium acetate, and at the same time, the lead dioxide physically embedded in the above-mentioned hyposulfite nodules becomes more easily accessible by the reactants and more rapidly reduced to lead oxide. The following reaction is related to the regeneration of high-purity lead from the electrode aggregate mucus of the waste lead battery. 201119946 Example of a compound Example wherein the sulfate vessel is a measured component in the impurity-containing starting material (close to about 60% by weight) and dissolved In an aqueous solution of sodium acetate. Reaction 1: Dissolving lead sulfate
PbS04 (不可溶)+4 CH3COONa->可溶解PbS04複合物 反應2:溶解氧化鉛 2CH3C00Na+H2S04->2CH3C00H+Na2S04PbS04 (insoluble) +4 CH3COONa->soluble PbS04 complex reaction 2: dissolved lead oxide 2CH3C00Na+H2S04->2CH3C00H+Na2S04
PbO (不可溶)+2CH3COOH+Pb(CH3COOH)2 (可溶解)+H20 Pb(CH3C00H)2+Na2S04+ PbS04 (不可溶)+2CH3CO〇Na PbS04 (不可溶)+4 CH3C00Na+可溶解PbS04複合物 反應3 ··使二氧化鉛還原及溶解 2CH3C00Na+H2S04^2CH3C00H+Na2S04 Pb02 (不可溶)+H202+ PbO (不可溶)+H20 + 1/2 〇2PbO (insoluble) +2CH3COOH+Pb(CH3COOH)2 (dissolvable)+H20 Pb(CH3C00H)2+Na2S04+ PbS04 (insoluble)+2CH3CO〇Na PbS04 (insoluble)+4 CH3C00Na+soluble PbS04 complex reaction 3 ··Reducing and dissolving lead dioxide 2CH3C00Na+H2S04^2CH3C00H+Na2S04 Pb02 (insoluble)+H202+ PbO (insoluble)+H20 + 1/2 〇2
PbO (不可溶)+2CH3CO〇h+ Pb(CH3COOH)2 (可溶解)+H2〇 Pb(CH3C00H)2+Na2S04·^ PbS04 (不可溶)+2CH3CO〇Na PbS04 (不可溶)+4 CH3C00Na+可溶解PbS04複合物 (選用)反應4 :使可能存在於含雜質起始材料中，且與雜質一 同分離之不可溶鉛化合物溶解，以再生此種較微量之鉛。PbO (insoluble) +2CH3CO〇h+ Pb(CH3COOH)2 (dissolvable)+H2〇Pb(CH3C00H)2+Na2S04·^ PbS04 (insoluble)+2CH3CO〇Na PbS04 (insoluble)+4 CH3C00Na+ soluble PbS04 Composite (optional) Reaction 4: The insoluble lead compound which may be present in the impurity-containing starting material and separated together with the impurities is dissolved to regenerate such a relatively small amount of lead.
PbO PbS04(^ Ti#)+12Na0H^5Na2Pb02(Ti#^)+Na2SO4+6H20 舉例而言，為處理回收自壓碎拋棄鉛電池之電極漿料黏液， 二•觀使用以濃度重量百料介於37.5至54.5%之溶解 將職水溶液。加入之硫酸總量係相當於或恰超過 雜質起始材料°二3^匕學計量需求量，其係由待處理含 中就化學計量需求預計算出之過氧化氳加入懸浮浴 中^還原内含於該起始材科中之二氧化錯。 汗 了於某-特定體積之溶液中處理之電極漿料量，係根據選定 201119946 醋酸鹽及加入硫酸之溶液中硫酸鉛溶解能力而定。該醋酸鹽溶液 之溶解硫酸鉛能力係根據其鹽類濃度而定。舉例而言，具有一醋 酸鈉濃度重量百分率37.5%之水溶液一公升，能夠溶解1〇〇公克之 硫酸鉛。藉由提高醋酸鹽之濃度，可溶解之硫酸鉛總量將成比例 地增加。可於該懸浮浴中進行上述反應之溫度係介於大約10〇c至 高達沸點之間。可藉一提桶或葉輪混合器來攪拌懸浮液，以利於 打碎鉛化合物聚集體。 選定操作條件之組合(起始固體材料之類型與細緻程度、硫酸 鉛溶解鹽溶液之類型與濃度、最終二氧化鉛還原劑添加物、溫度、 攪拌模式），將影響完成全濕式再生製程第一步驟(丨)所需之時間。 用於硫酸化該溶液中所有氧化鉛之硫酸，較佳地應具有一高濃 度，以不致過度稀釋該硫酸鉛溶解溶液。 一旦該反應時間可根據眾多參數之組合而大體上介於6至15 分鐘範圍之間時，即可例如藉過濾，將一含硫酸鉛之清澈醋酸溶 液與固相殘留物分離。所有不可溶雜質及物質，皆可因此與該溶 液分離(圖一之流程圖中之步驟2)。 於内含有呈硫酸錯形式之大致所有起始材料船内含物之清澈 醋酸溶液中實行之後績反應，可依據圖一之流程圖中步驟3之較 佳支型，將選疋與醋酸鹽（即細、钾或録)具相同陽離子之一氫氧化 物加入該溶液中，即可於確保溶液中所有鉛之沉澱係呈(黃色外觀) 氧化鉛(PbO)形式，而非呈（白色外觀)氳氧化鉛形式之一足夠高溫 度下，因氧化鉛之溶解度遠低於硫酸鉛，而產生一選擇性之氧化 鉛沈澱。一般而言，臨界溫度係於7〇t附近，因此可於大約72 至73t實行沈澱(除非基於某些理由，更希望回收一高度純化氫氧 化鉛，而其最終可熱轉化成氧化鉛）。 考慮圖一之流程圖表中步驟3之另一變型為，選定與醋酸鹽 201119946 具相同陽離子(即鈉、鉀、或銨)之一碳酸鹽取代一氫氧化物，將其 加入内含有呈硫酸鉛形式之大致所有起始材料鉛内含物之液體醋 酸溶液中，因遠低於硫酸鉛之溶解度，而產生碳酸鉛或碳酸鉛及 次碳酸鉛混合物之一選擇性沈澱。於本變型具體實施例中，可於 介於環境溫度至高達沸點之間之任何溫度下，實行沈澱。 一旦步驟3之反應完成，即可藉過濾（圖一之流程圖表中之步 驟4)將沈澱之氧化或氫氧化或碳酸/次碳酸鉛與該溶液分離，且同 時用於將鉛沈澱為不可溶氧化物(或氫氧化物)或碳酸鹽(及/或次碳 酸鹽)之氫氧化物或碳酸鹽之具相同陽離子之硫酸鹽，可仍保持於 該溶液中。 現亦内含有具相同陽離子之硫酸鹽之清澈醋酸溶液，可再循 環至製程中選擇性溶解硫酸鉛(步驟U之懸浮浴中，只要硫酸鹽之 含量仍保持於飽和以下(此限制主要係根據硫酸鉛溶解鹽溶液之類 型及處理狀態條件而定）。 當然’必須防止過量之硫酸鹽連同氧化或氫氧化或碳酸/次碳 酸鉛一同沈澱。因此，必須於遠於趨近飽和極限之前，即自該溶 液最終地排除過量之硫酸鹽（圖一之流程圖中之步驟8)。此可藉由 運用硫酸鹽（即硫酸鈉、鉀、銨者)於不同溫度下，不同於相對應醋 酸鹽者之溶解度，以選擇性地將該硫酸鹽結晶且使其與該醋酸溶 液分離，而輕易地達成。 可溶解鹽類之水溶液濃度及其實施硫酸鉛溶解時之溫度，因 僅影響完成上述反應所需之時間及可溶解於該溶液中之硫酸鉛 量’而非屬必要參數。實際上，若該溶解溶液於將已溶解之鉛沈 殿為氧化物或氫氧化物或碳酸鹽/次碳酸鹽後，即加以回收，且因 此藉一再循環溶液來作用，則需要愈來愈多次之再循環，以完成 一給定量硫酸錯之溶解。 11 201119946 已證明本案之新穎方式本身，極為適合於處理電極漿料黏 液，其中三個主要鉛化合物，亦即硫酸鉛、氧化鉛及二氧化鉛之 總量，可依大约重量百分率2%之變化範園，於一平均值附近波 動而此實際上將阻礙精確計算出硫酸溶液之用量，其可將存在 於該含雜質起始材料中之所有氧化鉛轉化成硫酸鹽。 然而，若於實行本案新穎方法時，偶然發生加入超過化學計 量所需總量之硫酸’則當藉加人與所選醋酸鹽具相同陽離子之一 氫氧化物或-碳酸鹽而雜純鉛化合物後，將因該毅中存有游 離尽U酸，而形成一過量之所添加化合物之陽離 係可完全相較於硫酸峨量。反之，若偶然發生加:少= 計量所需總量之魏，則將出魏化物不完全轉化成硫酸鹽，如 此當分_體雜質時，-殘留量之氧化物將仍不溶解料酷酸溶 視中H外地出現此種情形，僅需將該分離之_物質再次 加入該懸浮財’藉加人—過量硫酸加以最終轉化即可。 每當透明醋酸鹽溶液中之硫酸鹽濃度趨近飽和時，該溶液較 佳地可連續或_地渗㈣過填充有蟄合樹脂之—分離柱，以將 溶液中之任何殘留錯離子分離(圖一之流程圖中之步驟$，其後再 將落液冷卻至HTC以沉聽晶固相物質（圖__之流程圖中之步驟 (0，而此無酸鹽具相同陽離子之硫酸鹽馳成之結晶固相物質 :經回收(圖一之流程圖中之步驟7)。接著可將無該硫酸 鹽义透明醋酸鹽溶液再循環至，該含雜質起始材料之懸浮浴，且 同時該無鉛硫酸鹽將組成一具市場銷路之副產物。 以下將記述數個範例，其僅用於_本發明方法之各種可能 具體實施例，而無任何排除其他可能具體實施例之意。 範例1 可表示成金屬等效 80公克回收乾燥電極漿料，其具有72%， 12 201119946 物义一鉛内含物’該_係與三水醋酸鈉佔重量百分率37·5%之 剛〇毫升水雜，賴佔重量百料94至96%之122公 克添加物，於溫度83t下—_拌來進行處理。接著，將重量百 分率32%《過氧化氫緩慢地加至該懸浮液中(以液滴方式持續大約 10分鐘），直到不再清楚觀察到澄清懸浮液為止。 接著過滤㈣浮液，且經分離之固相物質係由不可溶之錯化 合物及純合物結核、電極餘碎片及用於製作電極漿料之例如 碳黑&酸鎖、纖、維等各種添加物，與例如沙粒、塑膠材料等雜 質組成此深灰色固相物質之總量，大約佔乾燥電極聚料固體塊 以重量百分率計之4至12%。 ,經過濾之含硫酸鉛清澈溶液，將加入氫氧化鈉， 於83°C下攪 掉’直到氧化㈣式之沈峡近完成為止。此後將麵該懸浮液， 使孩沈澱物與現在富含硫軸之醋咖溶解溶液相分離 ，該溶液 將再循環至攪拌硫酸财解容器中，只要該溶液中之硫酸鈉含量 仍保持於飽和以下即可。 、、當該醋酸鈉溶液中之硫酸鈉含量變為接近飽和極限時，將使 該洛液滲濾通過填充有螯合樹脂之一分離柱，該螯合樹脂係例如 商⑽型式名為Chelex-l〇〇或D〇wexA-l者，然可使用任何其他等 效樹脂。該樹脂填充劑可對殘留存於該硫酸鹽溶液中之極微量鉛 離子’幾乎完全地進行分離。 隨後’將純化之(幾近無鉛)硫酸鹽溶液於慢速攪拌下’緩慢地 冷卻至10C，以使硫酸鈉組成之一結晶固相物質沈澱，接著可藉 過遽該懸浮液來回收該結晶固相物質，且同時將透明溶液再循環 至該硫酸鉛溶解容器中。 可於160。(：下，使藉去離子水準確地沖洗之經過濾氧化鉛加熱 乾燥，只要達到重量恆定即可。 、 13 201119946 經分離之深灰色固相物質係於5〇t下，懸浮於重量八； 40%之氫氧化财15分鐘。經分離之清澈液相物質係加 ^ 硫酸鉛之清澈醋酸溶液中，作為所需氫氧化鈉總量之部份，、 考量存在於該溶液中呈競_之财身亦可轉化^或= 化)錯’以賴溶液巾之所絲皆沈澱為氧化錢氧 撼一 佳具體實補）。 ⑽象-較 於試驗終止時，記錄以下之平衡質量。 用於實驗之總量80公克回收電極漿料中，有4公克之深灰色 不可溶物質，其中内含有金屬鉛及例如沙粒、硫酸鋇及較少量其 他物質等無關物質。 、 可回收氧化鉛之計算最大量為62.05公克，而有效回收之氧化 錯量為62.03公克，回收產率為99.96%。 針對回收固體產物進行之化學分析可證實，其獨由99.99%純 度之氧化鉛(PbO)組成，而最終回收之硫酸鈉具有大約99.90%之純 度。 以下表格將總結詳述於上之範例1方法之其他四個範例具體 實施例之相關狀態條件、特點及結果，但其顯示出不同選擇之狀 態條件及獲致結果，其中恆使用回收自壓碎廢棄電池之同批電極 漿料作為起始材料。 編號 硫酸鉛溶 解溶液 反應時間 及溫度 沈澱化合物 獲致之純化 船化合物 產率 % 2 1000毫升 醋酸鋼 @,37.5% 10分鐘 65〇C NaOH Pb(0H)2 99.94 3 ——- 一 1000毫升 醋酸鋼 _ @40.0% 8分鐘 90°C NaOH PbO 99.95 1000毫升 醋酸鋼 J42.5% 12分鐘 45〇C Na2C〇3 PbC03 99.91 201119946 該氧化船(不論直接依全濕式製程製作或藉加熱全濕式製程所 製成之碳酸/次碳祕而獲致)㈣地適合於製備新電池之電極聚 料。 使用一鉛礦物或礦物混合物作為起始材料來實現本發明方法 者，可大致相似於上述具體實施例，而一必㈣先步驟係儘可能 將存在於礦物中之任何不鹽，轉化成硫酸鉛或氧她。例如， 對於方鉛礦，其為最普遍之鉛礦物，該礦物應依據一般之焙燒技 術，於空氣中加熱，直到亞硫酸鉛氧化成硫酸鹽為止。其他之常 見礦物硫酸錢本身已由硫酸鉛城’而無需任何預先處理。當 然’（多個)礦物應細磨，以利於其處理。 圖一係由廢棄錯電池及/或經最後細磨錄礦之回收電極漿料， 再生同純度化合物形式之錯之—工業設備可能具體實施例概略示 圖，其中該鉛礦最終將經預處理，以使同樣多之鉛化合物轉化成 硫酸錯。 圖二之圖解架構係提供上述製程變型之一多重具體實施例圖 不(然而，依據各變型，已將鈉指示為醋酸鹽與為沈澱所需之純鉛 化合物及選擇添加之化合物等二者之範例用選定陽離子）。 ,實際上，該設備大致需要三個攪拌與溫控反應器。含雜質材 料將於其内懸浮於一醋酸鹽水溶液中之一第一反應器RAC(l)，係 連附至一第一固液分離器珥1)，用於將内含硫酸鉛之溶液與該含 雜質起始材料中不可溶雜質所組成之固相物質相分離。 用於沈澱高純度船化合物，且為圖二之多重變型圖解架構中 反應器RAC(2)、RAC(3)與RAC(4)任一個之一第二反應器，係連 附至一第一固液分離器，該分離器為相關之一 F(2)、F(3)、與F(4)。 需要一第三且最後反應器RAC(5)及相連附之第三且最後固液 分離器F(5)’以至少週期性地(或更佳地呈連續地)處理再循環醋酸 15 201119946 鹽溶液’且將其再循環至第一硫酸鹽溶解反應器RACQ)。該處理 包括藉醋酸鹽與該醋酸鹽具相同陽離子之硫酸鹽間顯著不同之溶 解度，以選擇性地結晶，加入該第二反應器中以沈澱所需鉛化合 物及將其自系統中移除。必須(連續或間歇地)執行該步驟，以防止 再循環醋酸鹽溶液中相同陽離子之硫酸鹽發生飽和，若該飽和發 生，將造成該鹽連同硫酸鉛一同沈澱(致純化製程徒勞無益）。 依據較佳具體實施例，為確保「副產物」硫酸鹽(例如，硫酸 鈉）大致無鉛，且因此於經濟上具市場銷路，該設備可包含填充有 一合適螫合樹脂之一交換樹脂分離柱c(1)，當該溶液導向選擇性 之硫酸鹽結晶反應器RAC(5)時，該溶液將通過(不論連續或週期性 地)該樹脂分離柱，以針對可存在於該溶液中之殘留鉛離子進行分 離。 論然’該整合樹脂填充劑將逐步失去其活性，且必須週期性 地藉循環通過分離柱(C1)醋酸一段時間，以對經分離之鉛離子實施 一汽提。現在内含醋酸鉛，且用於週期性活化該交換樹脂之充斥 有鉛之醋酸汽提溶液，可藉僅將其加入第一反應器(中「 處理」，如相關標線所示者。 獲 圓二之多重具體實施例設備圖亦圖示出，於考量待處理含雜 質起始材料之組成物後認為有必要時，可選用反應器， 其中仍與經分離之固相雜質相結合之殘留量鉛係呈化合物或結核 其播法於弟一反應器R^c(i)處置該含雜質材料期間溶解。 ，經分離之固相物質係懸浮於，與選定醋酸鹽具相同陽離予之氫 虱化物熱濃縮溶液中，以溶解該些鉛化合物或其結核。依據一較 佳相實施例，相連附之液固分離器F(2bis)允許自溶有亞錯酸^ ^氳氧化物液射分離請有非轉質，雌餘化物液劑通 吊可用作為第二反應器RAC(2)或RAC(3)中氫氧化物添加物之一 201119946 部份’而用於賴溶射切有料賴減健錢氧化錯者。 【圖式簡單說明】 圓係本案方法主要步驟流程圖，用於由廢棄鉛電池電漿黏 液或鉛礦再生高純度氧化鉛，其可依卿地製賴賴/次碳酸 錯、或純氧化/氫氧化鉛。 圖一係一設備簡化示圖，其可依據圖一之選擇性製程流，由 廢，銘电池電漿黏液或錯礦，選擇性地再生如純碳酸/次碳酸船或 純氧化/氳氧化鉛之高純度鉛化合物。PbO PbS04(^ Ti#)+12Na0H^5Na2Pb02(Ti#^)+Na2SO4+6H20 For example, in order to treat the electrode slurry mucilage recovered from the crushed lead battery, the two are used in concentration and weight. 37.5 to 54.5% of the dissolved aqueous solution. The total amount of sulfuric acid added is equivalent to or just exceeds the impurity starting material. The amount of persulfate calculated from the stoichiometric demand in the to-be-treated content is added to the suspension bath. Dioxin in the starting material family. The amount of electrode slurry that has been treated in a certain volume of solution is determined by the ability to dissolve lead sulfate in the solution of 201119946 acetate and sulfuric acid. The ability of the acetate solution to dissolve lead sulfate depends on its salt concentration. For example, one liter of an aqueous solution having a concentration of sodium citrate of 37.5% by weight can dissolve 1 gram of lead sulfate. By increasing the concentration of the acetate, the total amount of soluble lead sulfate will increase proportionally. The temperature at which the above reaction can be carried out in the suspension bath is between about 10 〇c and up to the boiling point. The suspension can be stirred by a bucket or impeller mixer to facilitate breakage of lead compound aggregates. The combination of selected operating conditions (the type and fineness of the starting solid material, the type and concentration of lead sulfate dissolved salt solution, the final lead dioxide reductant additive, temperature, agitation mode) will affect the completion of the full wet regeneration process. The time required for one step (丨). The sulfuric acid used to sulfate all of the lead oxide in the solution preferably has a high concentration so as not to excessively dilute the lead sulfate dissolution solution. Once the reaction time can be substantially between 6 and 15 minutes depending on a combination of parameters, a clear acetic acid solution containing lead sulfate can be separated from the solid residue, for example by filtration. All insoluble impurities and substances can be separated from the solution (step 2 in the flow chart of Figure 1). The subsequent reaction is carried out in a clear acetic acid solution containing substantially all of the starting materials of the ship in the form of sulfuric acid. The selective reaction can be carried out according to the preferred support of step 3 in the flow chart of Figure 1. That is, fine, potassium or recorded) hydroxide with one of the same cations is added to the solution to ensure that all lead precipitates in the solution are in the form of (yellow appearance) lead oxide (PbO) rather than (white appearance). One of the forms of antimony oxide is sufficiently high that the solubility of lead oxide is much lower than that of lead sulfate, resulting in a selective lead oxide precipitation. In general, the critical temperature is around 7 〇t, so precipitation can be carried out at about 72 to 73 t (unless for some reason it is more desirable to recover a highly purified lead hydroxide which is ultimately thermally convertible to lead oxide). Consider another variation of step 3 in the flow chart of Figure 1. Select one of the same cations (i.e., sodium, potassium, or ammonium) as the carbonate, and replace it with a carbonate of 201119946, which is added to contain lead sulfate. The liquid acetic acid solution of the lead content of substantially all of the starting materials is selectively precipitated by one of a mixture of lead carbonate or lead carbonate and lead carbonate, which is much lower than the solubility of lead sulfate. In a specific embodiment of the present variation, precipitation can be carried out at any temperature between ambient temperature and boiling point. Once the reaction in step 3 is completed, the precipitated oxidized or oxidized or carbonic acid/lead carbonate can be separated from the solution by filtration (step 4 in the flow chart of Figure 1) and simultaneously used to precipitate lead as insoluble. The sulfate of the oxide or carbonate of the oxide (or hydroxide) or carbonate (and/or hypocarbonate) having the same cation may remain in the solution. It also contains a clear acetic acid solution with the same cation sulfate, which can be recycled to the process to selectively dissolve lead sulfate (in the suspension bath of step U, as long as the sulfate content remains below saturation) (this limitation is mainly based on Depending on the type of lead sulfate dissolved in the salt solution and the conditions of the treatment conditions. Of course, it is necessary to prevent excess sulfate from being precipitated together with oxidation or hydration or carbonic acid/lead carbonate. Therefore, it must be before the saturation limit is reached, ie Excess sulfate is finally removed from the solution (step 8 in the flow chart of Figure 1). This can be achieved by using sulfate (ie sodium sulfate, potassium, ammonium) at different temperatures, different from the corresponding acetate. The solubility of the sulphate is selectively achieved by selectively crystallizing the sulphate and separating it from the acetic acid solution. The concentration of the aqueous solution of the soluble salt and the temperature at which the lead sulphate is dissolved are affected only by the completion of the above reaction. The required time and the amount of lead sulfate soluble in the solution 'is not a necessary parameter. In fact, if the dissolved solution is in the dissolved lead After the compound or hydroxide or carbonate/carbonate is recovered, and thus acts as a recycle solution, more and more recycling is required to complete the dissolution of a given amount of sulfuric acid. 11 201119946 It has been proved that the novel way of the case itself is very suitable for treating the electrode slurry mucilage. The total amount of three main lead compounds, namely lead sulfate, lead oxide and lead dioxide, can vary according to the weight percentage of 2%. Fluctuating around the average value, which in fact will hinder the accurate calculation of the amount of sulfuric acid solution, which converts all of the lead oxide present in the impurity-containing starting material into a sulfate. However, if the novel method of the present invention is practiced At the time, the accidental occurrence of the addition of more than the stoichiometric amount of sulfuric acid', when the borrower and the selected acetate have the same cation as one of the hydroxide or -carbonate and the pure lead compound, will be saved There is a free U acid, and the cation system which forms an excess of the added compound can be completely compared with the amount of barium sulfate. Conversely, if it happens by chance: less = the total amount required for the measurement In the case of the incomplete conversion of the sulphate to the sulphate, so that when the _ body impurity is used, the residual amount of the oxide will still be insoluble in the sulphuric acid solution. This occurs in the H field, and only the separation is required. _ Substance is added to the suspension again, and the final conversion can be carried out by adding excess sulfuric acid. Whenever the sulfate concentration in the transparent acetate solution approaches saturation, the solution is preferably continuously or osmotically (four) overfilled. There is a separation column of the resin to separate any residual counter ions in the solution (step $ in the flow chart of Figure 1, and then the liquid is cooled to HTC to listen to the crystal solid phase material (Fig. __ The step in the flow chart (0, and the salt-free solid phase material obtained by the sulfate-free salt of the same cation: recovered (step 7 in the flow chart of Fig. 1). The clear acetate solution is recycled to the suspension bath containing the impurity starting material, and at the same time the lead-free sulfate will constitute a by-product of the market. Several examples will be described below, which are only used for various possible embodiments of the method of the present invention without any other specific embodiments being excluded. Example 1 can be expressed as a metal equivalent of 80 grams of recovered dry electrode slurry, which has 72%, 12 201119946. The meaning of a lead inclusion 'this _ series with sodium acetate trihydrate accounted for 37.5% by weight of 〇 〇 The water is mixed, and the weight is 94 to 96% of the 122 grams of the additive, which is mixed at a temperature of 83t. Next, a 32% by weight "hydrogen peroxide was slowly added to the suspension (for about 10 minutes in droplets) until a clear suspension was no longer clearly observed. Next, the (four) floating liquid is filtered, and the separated solid phase material is composed of insoluble wrong compound and pure compound tuberculosis, electrode residue fragments, and various materials such as carbon black & acid lock, fiber, and vitamin used for preparing the electrode slurry. The additive, which is composed of impurities such as sand particles, plastic materials and the like, constitutes the total amount of the dark gray solid phase material, which is about 4 to 12% by weight of the dry electrode aggregate solid block. The filtered lead sulfate-containing clear solution is added with sodium hydroxide and stirred at 83 ° C until the oxidation (4) type of the gorge is nearly completed. Thereafter, the suspension is surfaced to separate the child's sediment from the sulphuric acid-solvent solution which is now rich in sulfur. The solution is recycled to the stirred sulfuric acid storage vessel as long as the sodium sulfate content of the solution remains saturated. The following can be. When the sodium sulfate content in the sodium acetate solution becomes close to the saturation limit, the Loose solution is percolated through a separation column packed with a chelate resin such as the type of Chelex- L〇〇 or D〇wexA-l, but any other equivalent resin can be used. The resin filler can almost completely separate the extremely small amount of lead ions remaining in the sulfate solution. Subsequently, the purified (nearly lead-free) sulfate solution is slowly cooled to 10 C under slow agitation to precipitate a crystalline solid phase material of sodium sulfate composition, which can then be recovered by the suspension. The solid phase material is simultaneously recycled to the lead sulfate dissolution vessel. Available at 160. (:, the filtered lead oxide which is accurately washed by deionized water is heated and dried, as long as the weight is constant. 13, 201119946 The separated dark gray solid phase material is suspended at 5 〇t and suspended in the weight of 8; 40% of the hydrogenation for 15 minutes. The separated clear liquid substance is added to the clear acetic acid solution of lead sulfate as part of the total amount of sodium hydroxide required, and is considered to be present in the solution. The financial body can also be converted into ^ or = )) wrong's reliance on the solution of the towel is precipitated as oxidized oxyhydroxide a good specific compensation). (10) Image - When the test is terminated, the following balance quality is recorded. The total amount of 80 g of the recovered electrode slurry used in the experiment was 4 g of dark gray insoluble matter containing metal lead and unrelated substances such as sand, barium sulfate and a smaller amount of other substances. The maximum amount of recoverable lead oxide is 62.05 grams, while the effective recovery is 62.03 grams, and the recovery yield is 99.96%. Chemical analysis of the recovered solid product confirmed that it consisted solely of 99.99% pure lead oxide (PbO), and the final recovered sodium sulfate had a purity of about 99.90%. The following table will summarize the relevant state conditions, characteristics and results of the other four example embodiments of the method of Example 1 above, but which show the state conditions and results obtained for different selections, where constant use is recycled from crushed waste. The same batch of electrode slurry of the battery was used as a starting material. No. Lead sulfate solution solution Reaction time and temperature Precipitated compound obtained yield of purified ship compound % 2 1000 ml of acetic acid steel @, 37.5% 10 minutes 65 〇 C NaOH Pb (0H) 2 99.94 3 ——- 1000 ml of acetic acid steel _ @40.0% 8 minutes 90°C NaOH PbO 99.95 1000ml Acetate Steel J42.5% 12 minutes 45〇C Na2C〇3 PbC03 99.91 201119946 The oxidation vessel (whether directly or in accordance with the full wet process or by heating the full wet process The carbonic acid/secondary carbon produced is obtained (4) and is suitable for preparing electrode aggregates for new batteries. The use of a lead mineral or mineral mixture as a starting material to carry out the process of the present invention can be substantially similar to the specific embodiment described above, and a mandatory (four) first step is to convert any non-salt present in the mineral to lead sulfate as much as possible. Or oxygen her. For example, for galena, it is the most common lead mineral, which should be heated in air according to general roasting techniques until the sulphite is oxidized to sulfate. Other common mineral sulphuric acid money itself has been made from lead sulphate' without any prior treatment. Of course, the mineral(s) should be finely ground to facilitate its handling. Figure 1 is a schematic diagram of a specific embodiment of an industrial device that can be reprocessed by recycling a faulty battery and/or recovering an electrode slurry by final fine grinding, in the form of a compound of the same purity. The lead ore will eventually be pretreated. To convert as many lead compounds into sulfuric acid. The schematic architecture of Figure 2 provides one of the above-described process variants. Multiple embodiments are shown (however, depending on the variant, sodium has been indicated as acetate and the pure lead compound required for precipitation and the selected compound, etc. The example uses the selected cation). In fact, the equipment generally requires three agitated and temperature controlled reactors. The first reactor RAC(l), which is suspended in an aqueous solution of an acetate, is attached to a first solid-liquid separator 珥1) for the solution containing lead sulfate The solid phase material composed of the insoluble impurities in the impurity-containing starting material is phase-separated. A second reactor for precipitating high-purity ship compounds and one of the reactors RAC (2), RAC (3) and RAC (4) in the multiple variant diagram architecture of Figure 2, attached to a first A solid-liquid separator, which is one of the related F(2), F(3), and F(4). Requires a third and final reactor RAC (5) and associated third and last solid-liquid separator F (5) ' to recycle the acetic acid at least periodically (or more preferably continuously) 15 201119946 salt The solution 'recycles it to the first sulfate dissolution reactor RACQ). The treatment comprises a significant difference in solubility between the acetate and the sulfate of the same cation of the acetate to selectively crystallize and be added to the second reactor to precipitate the desired lead compound and remove it from the system. This step must be carried out (continuously or intermittently) to prevent saturation of the sulfate of the same cation in the recycled acetate solution, and if this saturation occurs, the salt will be precipitated together with lead sulfate (the purification process is useless). According to a preferred embodiment, to ensure that the "by-product" sulfate (e.g., sodium sulfate) is substantially lead-free and therefore economically marketable, the apparatus may comprise an exchange resin separation column c filled with a suitable chelating resin. (1), when the solution is directed to the selective sulfate crystallization reactor RAC (5), the solution will pass (whether continuously or periodically) the resin separation column to target residual lead that may be present in the solution. Ions are separated. It is argued that the integrated resin filler will gradually lose its activity and must be periodically circulated through the separation column (C1) acetic acid for a period of time to effect a stripping of the separated lead ions. The lead acetate-containing stripping solution, which contains lead acetate and is used to periodically activate the exchange resin, can be added to the first reactor only by "processing", as indicated by the relevant markings. A multi-specific embodiment apparatus diagram also illustrates that a reactor may be used in consideration of the composition of the impurity-containing starting material to be treated, wherein the residual amount is still combined with the separated solid phase impurities. The lead system is a compound or nodules which is dissolved during the treatment of the impurity-containing material by the reactor R^c(i). The separated solid phase material is suspended in the same cation as the selected acetate. The telluride is heated to concentrate the solution to dissolve the lead compounds or their nodules. According to a preferred embodiment, the attached liquid-solid separator F(2bis) allows autolysis of the sub-acid acid oxide spray Separation, please have non-transfer quality, female remnant liquid can be used as one of the second reactor RAC (2) or RAC (3) hydroxide additive 201119946 part of the 'solar spray cut material Jian Qian oxidizes the wrong person. [Simple diagram of the diagram] The main steps of the method are used to regenerate high-purity lead oxide from the waste lead battery plasma mucilage or lead ore, which can be made by relying on the dialysis/secondary carbonic acid or pure oxidation/lead hydroxide. Simplified diagram, which can selectively regenerate high-purity lead compounds such as pure carbonic acid/carbonic acid ship or pure oxidized/bismuth oxide lead according to the selective process flow of Fig. 1, from waste battery, slurry or miscarrying. .