B7 五、發明説明（1 ) 發明背景 小型密閉式電池的應用消費市場主要爲家電用品類包 括可攜式收放音機：刮鬍刀、、手電筒\玩具：個人電腦與 其他消費性用品類等的使用，t估計未來的用量蔣會日漸增 加。.廢棄的小型密閉式家用電池會對環境造成污染，.主要 是由汞、、鎘等重金屬成份所引起。.廢棄的電池在未經回收 處理時，.通常會隨著垃圾被處理掉？ 一般的垃圾處理可以 分爲掩埋與焚化兩種：廢電池在經過長期的掩埋處理後，， 會因汞、、鎘等重金屬的釋出造成土壤的污染.。而廢電池於 垃圾焚化處理時，、更會由於金屬汞：鎘的沸點均低於8 00 °c，.造成汞、.鎘成份會在焚化爐的高溫（約1 000°c)變成 蒸氣而隨廢氣排放到大氣中，、對空氣造成污染ί未氣化的 重金屬成份則殘留在爐灰中，，隨著爐灰的進一步處理（掩 埋或塡土等）會面臨雨水的沖刷而溶入地下水或河水中.， 經濟部中央標準局員工消费合作社印製 (請先閲讀背面之注Ϊ項再填寫本頁) 造成水質的污染、，因此自然環境中的土壌：空氣，、水質均 有可能被未經回收處理的廢電池所污染，.近年來.，歐美曰 等先進國家；對於廢電池的處理均明確的立法管制：並且 持續的加強處理標準中。.於是如何開發出無污染且具經濟 性的電池回收技術，，是；目前各國努力追求的目標.。 家電用廢棄電池回收處理所遭遇的最大困難點，，在於 所回集的小型廢電池種類繁多：例如一次電池使用的錳 鋅：鹼錳等’、以及二次電池使用的鎳鍚、，鎳氫：鋰等電 池。、這些電池由外觀上很難爲一般使用者所判別區分？因 此在進行回收時通常是各式廢電池混合在一起的方式被回 -3 - 本纸张尺反適用中國國家標準（CNS ) Α4規格（210X297公釐） 經濟部中央標準局員工消费合作社印袋 A7 B7 i、發明説明（2 ) 收。.而所回收的混合各式廢電池：由於外觀大小相近/若 欲利用物理方法進行類別分選相當困難，.尤其是要達到合 乎經濟的要求更是難上加難：因此如何避免分類處理，，而 直接尋求一種各類型廢電池混合的適當回收處理方法，，是 比較符合目前廢電池回收處理技術的需求；· 目前已知的典型廢電池回收方法介紹說明如下.： (一） 德國 ALD Vacuum Technologies Gm bJH 開發的真空高溫爐中，.進行廢電池的水銀 '鎘、、鋅/鋰等 成份的回收處理，.由於整體系統必需在高溫與真空氣密條 件下運作，，使得設備變得十分繁雜與昂貴，，其操作亦繁複 不便：尤其是進行較大量的廢電池處理時：受限於大型高 溫真空氣密處理設備的昂貴與技術不易達成等問題.，更是 使得實際具經濟的商業化可行性大爲降低，。 (二） 瑞士 DECO-HANULIK AG開發的混合廢電 池回收方法，.採用旋轉爐逆向通氣；將經切碎的廢電池汞 齊等成份在高溫加熱下分解成水銀蒸氣，.再經過旋轉爐的 高溫氧化環境轉化成氧化物粒子，，最後再由逆向通氣將氧 化物粒子帶到熱濾器中收回收.，此法未採用真空操作，並 • φ 採用重油與煤炭加熱設備與操作的成本較低.，具有較高 的商業運作可能性，.但是對於多項成份（如汞：鎘、耗、、 鉛等）的匝收無法作分離.，僅能在熱濾器中將汞、.鎘，、 鋅、.鉛等氧化物混合在一起收集則是其缺點。B7 V. Description of the invention (1) Background of the invention The application of small sealed batteries The consumer market is mainly home appliances including portable radios: shavers, flashlights \ toys: personal computers and other consumer products, etc. The use of t is estimated to increase in the future. Discarded small, sealed home batteries will cause environmental pollution, mainly caused by mercury, cadmium and other heavy metals. When used batteries are not recycled, are they usually disposed of with garbage? General waste treatment can be divided into two types: landfill and incineration: After long-term landfill treatment of waste batteries, soil pollution will be caused by the release of heavy metals such as mercury, cadmium, etc. When waste batteries are incinerated, the mercury and cadmium components of the metal mercury: cadmium are lower than 8000 ° C, causing the mercury and cadmium components to become steam at the high temperature of the incinerator (about 1 000 ° c). As the exhaust gas is discharged into the atmosphere, it causes pollution to the air. Un-gasified heavy metal components remain in the furnace ash. With further processing of the furnace ash (burial or soil, etc.), it will be washed by the rainwater and dissolved into the groundwater Or river water. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back before filling out this page), causing pollution of water quality, so soil in the natural environment: air, water quality may be affected by Contaminated by waste batteries that have not been recycled. In recent years, Europe, America and other advanced countries have clear legislative controls on the disposal of waste batteries: and continue to strengthen the treatment standards. So how to develop a pollution-free and economical battery recycling technology is, at present, the goal that countries are striving for. The biggest difficulty encountered in the recovery and disposal of used batteries for home appliances lies in the large number of small waste batteries collected: for example, manganese and zinc used in primary batteries: alkaline manganese, etc., and nickel rhenium and nickel hydride used in secondary batteries. : Lithium and other batteries. 2. These batteries are difficult to distinguish by ordinary users from the appearance? Therefore, when recycling, various types of waste batteries are usually mixed back -3-This paper rule applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) The central government bureau of the Ministry of Economic Affairs Consumer Cooperative Printed Bag A7 B7 i. Description of the invention (2) Close. .Recycled mixed types of waste batteries: Due to their similar appearance and size, it is very difficult to use physical methods to sort the categories. Especially to meet the economic requirements is even more difficult: how to avoid classification, Directly seeking an appropriate recycling method for the mixing of various types of waste batteries is more in line with the requirements of current waste battery recycling technology; · The currently known typical methods of recycling waste batteries are described below: (1) ALD Vacuum, Germany In the vacuum high temperature furnace developed by Technologies Gm bJH, the mercury, cadmium, zinc / lithium and other components of the waste battery are recycled. Because the overall system must operate under high temperature and vacuum airtight conditions, the equipment becomes very It is complicated and expensive, and its operation is also complicated and inconvenient: especially when dealing with a large amount of waste batteries: limited by the large-scale high-temperature vacuum air-tight processing equipment, expensive and difficult to achieve technology, etc., which makes the actual economical business The feasibility of transformation has been greatly reduced. (2) Recycling method of mixed waste battery developed by DECO-HANULIK AG in Switzerland, adopts rotary furnace for reverse ventilation; decomposes chopped waste battery amalgam and other components into mercury vapor under high temperature heating, and then passes the high temperature of the rotary furnace. The oxidizing environment is converted into oxide particles, and finally the oxide particles are brought to the heat filter for recovery by reverse aeration. This method does not use vacuum operation, and • φ uses heavy oil and coal heating equipment and operation with low cost. It has a high possibility of commercial operation. However, it is impossible to separate the turns of many components (such as mercury: cadmium, energy, lead, etc.), and only mercury, cadmium, zinc, The mixing of oxides such as lead is a disadvantage.
(三） 其他的統合廢電池回收方法如德國的PIRA(3) Other integrated waste battery recycling methods such as PIRA in Germany
GmbH採用溼式回收處理法：整體製程非常的繁複\，包 ·. '· -4 - 本纸张尺反適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 括切碎、.磁選：篩選；酸溶i壓濾、*離子交換.、電解·、碳 酸化沉澱等等：設備的投資與操作成本均昂貴.，且各項產 品的品質不易控制，.另外荷蘭的TNO Process則採用 溼式的有機溶劑萃取分離方法，.整體製程亦非常的繁複,。 美國的Rayovac Corporation採用溼、·火法並用，先 t 利用高溫處理將水銀成份分離後，，再利用溼式的溶解分離 金屬，.製程亦顯得非常的崔複？ 發明要旨 本發明主要目的在於提供一種簡單有效的混合廢電池 回收處理方法，.可將廢棄的各類型家電用電池在不需經過 分類下直接進行處理而使得廢電池中所含的重金屬物質 被有效的還原分離並回收成各種單一的富集金屬物質，， 如鋅•、鎘：水銀：鋰等可再資源化產品.，且處理後的殘留 物質不再具有重金屬污染性.。 爲了達成上述目的.，一依照本發明內容而完成的混合 廢電〕池回收處理方法，.包含下列步驟.： a) 使混合廢電池處於一 1100-1200 °C還原氣氛中.， 而將混合廢電池中的金屬成分還原成元素態，·其中沸點高 於1 2 0 0 eC之鐵：錳、·鎳及鋰以固/液態底部產物形式被收 集，，而沸點低於1 1 0 0 °C之鋅：鎘、.汞等成分則以蒸氣形 式被導入於） b) — 800-900 °C還原氣氛中.，於是沸點高於900 〇c之 鋅以液態底部產物被收集.，而沸點低於80〇。(：之鎘：汞等 -5 - 本纸张尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 11·1 1!111 ——.^1 I \ 农 I I (請先閲讀背面之注意事項再填寫本頁) 訂 A7 B7 經濟部中央標隼局員工消費合作社印製 五、發明説明（4 ) 成分則以蒸.氣形式被導入於.' C) — 550-750 °C還原氣氛中：於是沸點於750 °C之鎘 以液態底部產物被收集，.而沸點低於5 5 0 °C之汞等成分則 以蒸氣形式被導入於. d) — 2 5 0 - 3 5 0 °C還原氣氛中，.於是沸點高於35〇°C之 汞以液態底部產物被收集：而與沸點低於2 5 0 °C之不含金 ^屬成分之蒸氣分離。. 較佳的，步驟a)被取代爲：使混合廢電池處於一 1350-1450 °C還原氣氛中，.而將混合廢電池中的金屬成 分還原成元素態：其中沸點高於1 4 5 0 °C之鐵、.錳及鎳以 固/液態底部產物形式被收集等：而沸點低於1 3 5 0 °C之 鋰、.鋅：鎘：汞等成分則以蒸氣形式被導入於一 1 00 0-1 2 00 °C還原氣氛中：於是沸點高於1 200°C之鋰以液態底 部產物形式被收集，.而沸點低於1 0 0 0 °C之鋅：鎘.、汞等 成分則以蒸氣形式被導入於步驟b)之800-900 °C還原氣 氛中接著進行後續步驟/ 較佳的，.步驟d)之不含金屬成分之蒸氣被導入於一 100-200 °C還原氣氛中而使得其中之成分呈還原態，、其中 沸點或熔點低於1 0 0 °C者以液或固態底部库物形式被收 集，，而沸點低於l〇〇°C者則被導入一水氣冷凝器中•，於該 冷凝器中冷凝出其中的水份.，並將未凝結的氣體混合物導 入一廢氣洗滌塔中進行處理再排出、。 較佳的，該等高溫的還原氣氛係於一密閉串聯式的高 溫還原窯中形成，t其中每一窯分別被導入瓦斯與空氣進行 ---------''装— (請先閲讀背面之注意事項再填寫本頁) 本纸张尺度適用中國國家標準（CNS ) Μ規格（2ΐ〇χ297公釐） Α7 Β7 經濟部中央標率局貝工消费合作社印製 五、發明説明（5 ) 燃燒，·並控制瓦斯與空氣的流量，，而產生具有想要的高溫 及具還原性的一氧化碳氣體之高溫還原氣氛；其中瓦斯與 空氣之流量比介於1 : 3到1 : 1(體積）並藉由觀察燃燒火 燄之顏色或藉由使用一氣體濃度檢測器量測各持溫窯內的 一氧化碳濃度而調整該流量比； 上述本發明方法是一種簡單有效的混合廢電池回收處 理方法，、其中欲回收之金屬化合物在高溫下直接與還原氣 體（主要爲一氧化碳）充分接觸並進行還原反應.，而有效還 原成金屬元素，，並藉由串聯分段式的冷凝：可以將廢電池 中所含的金屬物質回收成各種單一的富集金屬物質.，如 鋰、、鋅：鎘.、水銀等再資源化產品1而且處理後的殘留物 質亦不再具有重金屬污染：於是可避免先前技藝中對多項 成份（如汞、鎘、辞、鉛等）®令一嗥0噑哮垮作兮f昨哮 再者，.本發明方法係於常壓操作，.可避免先前技藝中 在真空條件下進行操作的缺點.，而且整體操作亦適合進行 大量連續式的廢電池處理：更具有經濟可行性.。 圖示之簡單說明 圖1爲本發明之第-1較佳具體實施例的示意流程圖。 圖2爲本發明之第較佳-具體實施例的示意流程圖。 發明之詳細說明 本發明爲一種混合廢電池的高溫回收處理方法，.可以 (請先閲讀背面之注意事項再填窝本頁) 裝. 、11 本纸张尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 B7 經濟部中央標準局貞工消費合作社印製 五、發明説明（） 不需經過分類處理將各類型廢棄家電用電池，.例如錳鋅.、 鹼錳、·氧化銀：水銀：鎳鎘、.鎳氫.、鋰等電池.，以混合方 式直接進行回收處理.，於是可避免繁複不經濟的分選作 業，.符合現行廢電池回收處理技術發展的最新趨勢。.廢電 池經由本發明處理後可以回收成各種單一的富集金屬物 質，，如鋅、.鎘、.水銀、鋰等再資源化產品.。 ^ ΰ 一適合使用於本發明方法之混合廢電池回收處理裝置 如圖1所示，.主要的構造是由數個串聯的高溫瓦斯還原持 溫窯10、、20、.30、.40、.50以及水氣冷凝器60與廢氣洗 滌塔70組合而成j各持溫窯的基本構造分別包括主體.、底 部產物排放口 150 .、還原氣氛與控溫輔助器1〇〇以及持溫 窯間的連接道120等：其中起始的主持溫窯10尙連結有一 密閉式的混合電池進料器20 0,與主要加熱源的瓦斯還原燄 噴入器1 1 0 V 混合廢電池是由該密閉式進料器200送入該主持溫窯 10內’（同時該瓦斯還原燄噴入器110及還原氣氛與控溫輔 助器100均經由一噴入口將瓦斯與空氣噴入主持溫窯10中 燃燒而產生一還原燄130進行加熱與控溫（1100_ 1200°C) '並在高溫下調整瓦斯與空氣的混合流量比、，將 窯內控制成高溫還原氣氛（亦即在高溫環境下、，使瓦斯的 碳氫化合物燃燒不完全：而產生具還原性的一氧化碳氣 體）’、使廢電池中的欲回收物質（尤指金屬化合物）在高溫 環境下直接與還原氣體（主要爲一氧化碳）充分接觸，、而持 續產生高溫還原反應，，將欲回收之金屬化合物镡原成元素 (請先閲讀背面之注意事項再填寫本頁) 装. 本紙张尺度適用中國國家標準（CNS ) A4規格（210Χ297公楚;> A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（7 ) 態金屬，、再藉由高溫（1 100-1 2 00°C)環境將沸點低於 1100°C的鋅、.鎘、.水銀等元素態金屬蒸發成氣相物質，， 並隨著燃燒氣的氣流帶往次一較低溫（800-900 °C)的持 溫窯2 0 而沸點高於1 2 0 0 °C之鐵、.錳、.鎳及鋰以固/液態 底部產物形式經由該底部產物排出口 150被收集。，在隨後 的各持溫窯20、，3 0及40中，、分別以該還原氣氛與控溫輔 助器100將窯內禮制成不同溫度的高溫還原氣氛，，於是在 溫度被控制在8 0 0 - 9 0 0 ° C的持溫窯2 0 ,,以液態底部產物 形式經由該底部產物排出口 150收集富於鋅的差物,。在溫 度被控制在5 5 0 - 7 5 0 ° C的持溫窯3 0，，以液態底部產物形 式經由該底部產物排出口 150收集富於鎘的產物,。在溫度 被控制在2 5 0 - 3 5 0 ° C的持溫窯4 0，，以液態底部產物形式 經由該底部產物排出口 150收集富於汞的產物 從持溫窯4 0頂部出來的、，沸點低於2 5 0 °C之不含金屬 成分的蒸氣被導入於一持溫窯40,.並以該還原氣氛與控溫 輔助器100將窯內控制成100_200 °C的還原氣氛，.而使得 其中主要爲有機物之成分呈還原態，，其中沸點或熔點低於 100 °C者以液或固態有機物底部產物形式經由該底部產物 排出口 1 5 0被收集，、而沸點低於1 0 0 °C之成分所形成的蒸 氣則被導入一水氣冷凝器60中，.於其中冷凝出所含的水份 由底部廢水排放口 160排出，.並將未凝結的氣體混合物導 入一廢氣洗滌塔70中進行洗氣再以廢氣形式排出.。 由於本發明是採用密閉串聯式的高溫瓦斯還原窯系統 設計，、溫度的分佈是由起始進料的最高溫主持溫窯漸次降 -9 - ---------—裝— (請先閱讀背面之注^^項再填寫本頁) 訂 本认张尺度適用中國國家標準（CNS > A4規格（210X 297公釐） A7 B7 經濟部中央標準局員工消费合作社印製 五、發明説明（8 ) 至室溫的廢氣排放口、，因此可以發揮能源最有效利用、。隨 後的各持溫窯藉由還原氣氛與控溫輔助器100的控制、，可 使次一持溫窯的溫度較先前持溫窯低、，因此可使各金屬物 質的％素蒸氣隨著凝結溫度的差異而分離、。亦即當混合廢 電池經由密閉式進料器200進入主持溫窯10時，，各種欲回 收之金屬化合物均會在高溫還原氣氛下被還原成金屬氣態 蒸氣 i 如 As(g)Zn(g)、'Cd(g) : Hg(g)等.，隨後在各 個不同溫度的持溫窯中會漸次的凝結成液體態而被富集，， 當富集金屬液體達一定的液位時.，再個別經由產物排出口 釋出f 由於混合廢電池在主持溫窯10中經過充分的高溫還原 處理，.各種欲回收之金屬物質（如鋅、鎘、水銀、砷、鋰 等）均會呈氣態而蒸發分離去除.，因此在主持溫窯中的底 部產物僅爲較高沸點物質，，如鎳，、錳、.鐵與鋰等（，經底部 排放口 150排出時.，已不再具有其它污染性物質.，可以供 作煉鋼廠的原料應用？而隨後的各個持溫窯所回收的富集 金屬產品，，可能會含有因沸點溫域相近的雜質，.例如金屬 鋅的沸點爲9 0 7 °C :鋅富集持溫窯的溫度控制範圍約在 8 0 0〜9 0 0 °C之間，，部份沸點相近物質可能會有小部分同 時凝聚例如鈉（沸點爲8 8 0 °C )，.此點可視富集物質的最 終用途與目的，•再進一步考量再作精餾或純化$ 當小型密閉式混合廢電池經由密閉式進料器2 0 0進料 到主持溫窯10(溫度約1100〜1200。〇時.，由於瞬間的高 熱會迫使電池內部的電解液體因氣化而膨脹.，並導致整只 -1 0 - —.— — •— — — — 1. 裝— I I |打 (請先閱讀背面之注意事項再填寫本頁) 本纸张尺反適用中國國家標準（CNS ) A4規格（2丨〇χ29·7公瘦） A7 B7 經濟部中央標率局負工消費合作社印製 五、發明説明（9 ) 電池爆烈開來，、此點有利於電池內部物質的暴•.露與反應.， 有效的替代了一般使用的切碎預處理方式·。 本發明裝置由於是在常壓下使用瓦斯加熱處理.，因此 整體裝置並不需考慮昂貴的真空氣密功能，.此點可大幅降 低設備的投資成本，.並有效提升了操作的簡單與便利性.。 前述有關圖1之流程係不考慮鋰的回收：若混合廢電 池中含有廢鋰電池則可以依本發明另一較佳具體實施例來 進行鋰的進一步回收.。此另一較佳具體實施例可使用如圖 2所示之裝置進行，.圖2之裝置除了主持溫窯10’的操作溫 度控制在1 3 5 0 - 1 4 5 0 °C ,，及多設了 一用於回收鋰之持溫 窯15外均與圖1所示者相同.。 於主持溫窯10’中混合廢電池處於一1350-14 5 0 °C還 原氣氛中，.而將混合廢電池中的金屬成分還原成元素態， 其中沸點高於1 4 5 0 °C之鐵.、錳及鎳以固/液態底部產物形 式被收集等，.而沸點低於13 5(TC之鋰、.鋅、.釋、.汞等成 分則以蒸氣形式被導入於該持溫窯1 5於控制在'1 0 0 0 -1200 °C還原氣氛中：於是沸點高於1200 °C之鋰以液態底 部產物形式被收集，.而沸點低於1 0 0 0 °C之鋅、^鎘 '汞等 成分則以蒸氣形式被導入於該持溫窯20接著進行如同圖1 之流程的後續步驟.。 本發明內容可-以藉由以下實施例被進一步說明.，該等 實施例僅作爲說明之用.，而非用於限制本發明範圍.。除非 另外指明，.否則該等實施例中之百分比係以重量爲基準，。 ^1. -- n ml n - - ·1 ϋ_ι I m (請先閱讀背面之注意事項再填寫本頁) 本紙乐尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） Α7 Β7 五、發明説明（） <實施例> 取家電用廢棄混合電池15公斤.（包括錳鋅、鹼錳、 氧化銀、水銀、鎳_、鎳氬電池等）’.置入一主持溫黛 中，.主要的欲回收富集金屬物質，，包括水銀（沸點3 5 6 °C)、，鎘（沸點76 7 °C)、·鋅（沸點90 7 °C)等/分別以一還 原氣氛與控溫輔助器將各持溫窯窯內控制成不同溫度的高 溫還原氣氛，.溫度控制設定範圍分別爲主持溫窯 1 1 0 0〜1 2 0 0 t :鋅富集持溫窯8 0 0〜9 .0 0 t：、.鎘富集持 溫窯550~750 °C、.水銀富集持溫窯250〜300 °C.、有機 物質富集持溫窯100~200 °C :該還原氣氛與控溫輔助器 經由一噴入口將瓦斯與空氣噴入各持溫窯中燃燒 >，並調整 瓦斯與空氣的混合流量比（約_ 1:3到1:1)而產生一還原 燄，.將窯內控制成高溫還原氣氛（可利用燄色觀察作硏判 調整），廢電池在主持溫窯中經1小時高溫處理後^由底 部排放口釋出的底部產物主要爲鎳：錳、鐵等金屬，其 汞：鎘.、砷的含量均低於1 . 0 P P Μ，並在各持溫窯分別 收集到富於鋅、·鎘及汞的底部產物？ ----------> 裝—-----1Τ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標率局員工消费合作社印製 本纸张尺度適用中國國家標準（CNS ) Α4規格（210Χ297公董）GmbH adopts wet recycling method: the whole process is very complicated, and the package is ..-·-4-This paper rule applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back first) (Fill in this page) Order printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (3) Including shredding, magnetic separation: screening; acid-soluble pressure filtration, * ion exchange., Electrolysis, carbonation precipitation Wait: equipment investment and operating costs are expensive, and the quality of each product is not easy to control. In addition, the TNO Process in the Netherlands uses a wet organic solvent extraction and separation method. The overall process is also very complicated. The Rayovac Corporation in the United States uses a combination of wet and fire methods. After the mercury components are separated by high temperature treatment, the metals are dissolved by wet dissolution. The process is also very Cui Fu? Summary of the invention The main purpose of the present invention is to provide a simple and effective method for recycling and treating mixed waste batteries. The various types of household electrical appliances can be directly processed without classification and the heavy metal substances contained in the waste batteries can be effectively used. It can be separated and recovered into various single enriched metal substances, such as zinc •, cadmium: mercury: lithium and other recyclable products, and the residues after treatment are no longer polluting with heavy metals. In order to achieve the above object, a method for recovering and treating a hybrid waste electricity battery according to the present invention includes the following steps: a) The hybrid waste battery is placed in a reducing atmosphere of 1100-1200 ° C, and the mixture is mixed. The metal components in the waste battery are reduced to the elemental state. Iron in which the boiling point is higher than 1 2 0 eC: Manganese, nickel and lithium are collected as solid / liquid bottom products, and the boiling point is lower than 1 1 0 0 ° C zinc: cadmium, mercury and other components are introduced in the form of vapor) b) — 800-900 ° C reducing atmosphere. So the zinc with a boiling point higher than 900 ℃ is collected as a liquid bottom product, and the boiling point Less than 80. (: Cadmium: Mercury, etc.-5-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 11 · 1 1! 111 ——. ^ 1 I \ Nong II (Please read the precautions on the back first) Refill this page) Order A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4) The ingredients are introduced in the form of steam and gas. C) — 550-750 ° C reducing atmosphere: Therefore, cadmium with a boiling point of 750 ° C is collected as a liquid bottom product, and components such as mercury with a boiling point below 5 50 ° C are introduced in the form of vapor. D) — 2 5 0-3 5 0 ° C reduction In the atmosphere, the mercury with a boiling point higher than 35 ° C is collected as a liquid bottom product: it is separated from the metal-free vapors with a boiling point lower than 250 ° C. Preferably, step a) is replaced by: placing the hybrid waste battery in a reducing atmosphere of 1350-1450 ° C, and reducing the metal components in the hybrid waste battery to an elemental state: wherein the boiling point is higher than 1 4 5 0 Iron, manganese and nickel at ° C are collected in the form of solid / liquid bottom products, while lithium, zinc, cadmium: mercury and other components with boiling points below 1 350 ° C are introduced in the form of vapor. 00 0-1 2 00 ° C in a reducing atmosphere: then lithium with a boiling point above 1 200 ° C is collected as a liquid bottom product, while zinc with a boiling point below 100 ° C: cadmium, mercury and other components Then, it is introduced into the reducing atmosphere of 800-900 ° C in step b) in the form of steam, and then the subsequent step / preferably, the vapor containing no metal component in step d) is introduced into a reducing atmosphere of 100-200 ° C. It makes the components in a reduced state, and those whose boiling point or melting point is lower than 100 ° C are collected as liquid or solid bottom storage, and those whose boiling point is lower than 100 ° C are introduced into water. Gas condenser •, condenses out the water in the condenser, and leads the uncondensed gas mixture to an exhaust gas scrubber For processing and then discharged. Preferably, these high-temperature reducing atmospheres are formed in a closed series high-temperature reducing kiln, where each kiln is introduced with gas and air separately -------- '' (Please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) M specification (2 × 297 × 297 mm) Α7 Β7 Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ) Combustion, and control the flow of gas and air to produce a high-temperature reducing atmosphere with the desired high temperature and reducing carbon monoxide gas; where the flow ratio of gas to air is between 1: 3 to 1: 1 (volume ) And adjust the flow ratio by observing the color of the combustion flame or by measuring the carbon monoxide concentration in each temperature-holding kiln using a gas concentration detector; the method of the present invention described above is a simple and effective method for recycling and treating mixed waste batteries, The metal compound to be recovered is directly contacted with a reducing gas (mainly carbon monoxide) at a high temperature and undergoes a reduction reaction, and is effectively reduced to a metal element, and is separated in series by Condensing in stages: metal materials contained in waste batteries can be recovered into various single enriched metal materials, such as lithium, zinc: cadmium, mercury and other recyclable products1 and the residual materials after treatment are not There is heavy metal pollution again: so it can avoid a number of ingredients (such as mercury, cadmium, rhenium, lead, etc.) in the previous technology. It can avoid the disadvantages of operating under vacuum conditions in the prior art, and the overall operation is also suitable for a large number of continuous waste battery treatment: it is more economically feasible. Brief Description of the Drawings Fig. 1 is a schematic flowchart of the -1st preferred embodiment of the present invention. FIG. 2 is a schematic flowchart of a first preferred embodiment of the present invention. Detailed description of the invention The present invention is a high-temperature recycling treatment method for hybrid waste batteries. It can be installed (please read the precautions on the back before filling this page). 11 This paper size is applicable to China National Standard (CNS) Α4 specifications ( 210 × 297 mm) A7 B7 Printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () Various types of waste household appliances batteries, such as manganese zinc, alkali manganese, silver oxide: mercury, without classification treatment : Nickel-cadmium, nickel-metal hydride, lithium and other batteries are directly recycled in a mixed manner. Therefore, complicated and uneconomical sorting operations can be avoided, which is in line with the latest trend of the current development of waste battery recycling technology. The waste battery can be recycled into various single enriched metal materials, such as zinc, cadmium, mercury, lithium, and other re-resourced products after the treatment of the present invention. ^ ΰ A hybrid waste battery recovery and treatment device suitable for use in the method of the present invention is shown in Figure 1. The main structure is a series of high-temperature gas reduction and holding kiln 10, 20, .30, .40, etc. 50 and the water-gas condenser 60 combined with the exhaust gas washing tower 70. The basic structure of each temperature-holding kiln includes the main body, the bottom product discharge port 150, the reducing atmosphere and temperature control assistant 100, and the temperature-holding kiln. The connecting channel 120, etc .: Among them, the first host, the temperature kiln 10 尙, is connected with a closed hybrid battery feeder 20 0, and the main heating source gas reducing flame injector 1 1 0 V. The mixed waste battery is sealed by the closed Type feeder 200 is fed into the host kiln 10 (At the same time, the gas reduction flame injector 110 and the reduction atmosphere and temperature control assistant 100 all spray gas and air into the host kiln 10 through a spray inlet for combustion A reducing flame 130 is generated for heating and temperature control (1100_ 1200 ° C), and adjusting the mixed flow rate of gas and air at high temperature to control the inside of the kiln to a high-temperature reducing atmosphere (that is, in a high-temperature environment, so that Incomplete combustion of gaseous hydrocarbons: and Bioreducing carbon monoxide gas) ', the substance to be recovered (especially metal compounds) in the waste battery is brought into full direct contact with the reducing gas (mainly carbon monoxide) in a high temperature environment, and a high temperature reduction reaction continues, The metal compound to be recovered is the original element (please read the precautions on the back before filling in this page). This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 Gongchu; > A7 B7 Central Bureau of Standards, Ministry of Economic Affairs) Printed by the employee consumer cooperative. 5. Invention description (7) state metals, and zinc, cadmium, mercury, and other elemental metals with a boiling point lower than 1100 ° C in a high temperature (1 100-1 200 ° C) environment. Evaporates into a gaseous substance, and moves to the next lower temperature (800-900 ° C) temperature-holding kiln 20 with the gas stream of the combustion gas, and iron, manganese, boiling point higher than 12 0 ° C. Nickel and lithium are collected in the form of a solid / liquid bottom product through the bottom product discharge port 150. In the subsequent temperature-holding kiln 20, 30, and 40, the reducing atmosphere and the temperature control auxiliary device 100 will be used respectively. High-temperature reducing gas with different temperatures in the kiln Atmosphere, then in a temperature-controlled kiln 20 controlled at a temperature of 800-900 ° C, the zinc-rich difference is collected as a liquid bottom product through the bottom product discharge port 150. The temperature-controlled kiln 30 controlled at 5 0-7 5 0 ° C collects cadmium-rich products in the form of a liquid bottom product through the bottom product discharge port 150. The temperature is controlled at 2 5 0-3 5 The temperature-holding kiln 40 at 0 ° C collects mercury-rich products in the form of a liquid bottom product through the bottom product discharge port 150, and the boiling point is lower than 250 ° C. The vapor containing metal components is introduced into a temperature-holding kiln 40, and the reducing atmosphere and the temperature control assistant 100 are used to control the inside of the kiln to a reducing atmosphere of 100-200 ° C, so that the components mainly containing organic substances are in a reduced state. , Where the boiling point or melting point is lower than 100 ° C is collected as liquid or solid organic bottom products through the bottom product outlet port 150, and the vapor formed by components with boiling points below 100 ° C is collected Into a water-vapor condenser 60, the water contained in the condensate is condensed by the bottom Discharge port 160 is discharged. Uncondensed gas mixture and introduced into a gas scrubber for scrubbing column 70 and discharged in the form of exhaust gas .. Since the present invention adopts a closed series high-temperature gas reduction kiln system design, the temperature distribution is controlled by the highest temperature of the initial feed, and the temperature kiln is gradually lowered by -9-----------equipment-( Please read the notes on the back ^^ before filling out this page) The size of the acknowledgment is applicable to Chinese national standards (CNS > A4 size (210X 297 mm) A7 B7 Note (8) that the exhaust gas outlet to room temperature can be used to make the most efficient use of energy. The subsequent temperature-holding kilns can be controlled by the reducing atmosphere and the temperature control aid 100 to make the The temperature is lower than the previous temperature-holding kiln, so the% vapour of each metal substance can be separated according to the difference in condensation temperature. That is, when the mixed waste battery enters the temperature-controlling kiln 10 through the closed feeder 200, Various metal compounds to be recovered will be reduced to metal gaseous vapours such as As (g) Zn (g), 'Cd (g): Hg (g), etc. under a high-temperature reducing atmosphere, and then held at different temperatures. The kiln will gradually condense into a liquid state and be enriched. When the metal liquid reaches a certain level, it will be released separately through the product discharge port. Since the mixed waste battery has undergone sufficient high temperature reduction treatment in the host kiln 10, various metal substances (such as zinc, cadmium, mercury) to be recovered , Arsenic, lithium, etc.) will be in a gaseous state and removed by evaporation. Therefore, the bottom products in the host kiln are only higher boiling substances, such as nickel, manganese, iron and lithium, etc. (through the bottom discharge port When it is discharged at 150, it no longer has other polluting substances. Can it be used as a raw material for steelmaking plants? The subsequent enriched metal products recovered by each temperature-holding kiln may contain similar boiling point temperature ranges. Impurities. For example, the boiling point of zinc metal is 9 7 ° C: The temperature control range of the zinc-enriched temperature-holding kiln is between 8 0 and 9 0 ° C. Some materials with similar boiling points may have a small part. Simultaneously condensate, for example, sodium (boiling point is 880 ° C). This point can be based on the end use and purpose of the enriched substance. • Consider further rectification or purification. When small closed mixed waste batteries pass through closed feed The feeder 2 0 0 feeds to the host kiln 10 (Wen The temperature is about 1100 ~ 1200. 0:00. Due to the instantaneous high heat, the electrolyte body inside the battery will be forced to swell due to gasification, and the entire -1 0-—. — — • — — — — 1. Installation — II | Tap (Please read the precautions on the back before filling this page) This paper rule applies the Chinese National Standard (CNS) A4 specification (2 丨 〇χ29 · 7 thin) A7 B7 Offical Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed 5. Description of the invention (9) The battery exploded. This is conducive to the explosion of material inside the battery. Exposure and reaction. It effectively replaces the shredding pretreatment method commonly used. Because the device of the present invention uses gas heating treatment under normal pressure, the overall device does not need to consider the expensive vacuum airtight function. This can greatly reduce the investment cost of the equipment, and effectively improve the simplicity and convenience of operation Sex ... The foregoing process of FIG. 1 does not consider the recovery of lithium: if the mixed waste battery contains a waste lithium battery, further lithium can be recovered according to another preferred embodiment of the present invention. This another preferred embodiment can be carried out by using the device shown in FIG. 2. In addition to controlling the operating temperature of the temperature kiln 10 ', the device of FIG. 2 is controlled at 1350-1450 ° C, and more A temperature-maintaining kiln 15 for recovering lithium is provided as shown in FIG. 1. In the host 10 'of the temperature kiln, the mixed waste battery was placed in a reducing atmosphere of 1350-14 5 0 ° C, and the metal components in the mixed waste battery were reduced to the elemental state, in which the iron having a boiling point higher than 1 450 ° C Manganese and nickel are collected in the form of solid / liquid bottom products, while components with a boiling point lower than 13 5 (TC, lithium, zinc, release, mercury, etc. are introduced into the temperature-maintaining kiln 1 5 Controlled in a reducing atmosphere of '1 0 0 0-1200 ° C: Then lithium with a boiling point above 1200 ° C is collected as a liquid bottom product, while zinc and cadmium with a boiling point below 100 0 ° C 'Mercury and other components are introduced into the temperature-holding kiln 20 in the form of steam, and then the subsequent steps of the process as shown in FIG. 1 are described. The present invention can be further explained by the following examples. These examples are only used as For illustrative purposes, and not for limiting the scope of the present invention. Unless otherwise specified, percentages in these examples are based on weight. ^ 1.-N ml n--· 1 ϋ_ι I m (Please read the notes on the back before filling this page) The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297) ） Α7 Β7 V. Description of the invention () < Examples > Take 15 kg of waste hybrid batteries for household appliances. (Including manganese zinc, alkaline manganese, silver oxide, mercury, nickel, nickel-argon batteries, etc.) '. Moderator Wen Daizhong, the main metal materials to be recovered and enriched, including mercury (boiling point 3 56 ° C), cadmium (boiling point 76 7 ° C), zinc (boiling point 90 7 ° C), etc. Atmosphere and temperature control assistant control the temperature-reducing atmosphere in each temperature-holding kiln to different temperatures. The temperature control setting range is to host the temperature-kiln 1 1 0 0 ~ 1 2 0 0 t: zinc enriched temperature-holding kiln 8 0 0 ~ 9 .0 0 t :, cadmium-enriched holding kiln 550 ~ 750 ° C, mercury-enriched holding kiln 250 ~ 300 ° C, organic matter enriched holding kiln 100 ~ 200 ° C: The reducing atmosphere and the temperature control assistant spray gas and air into each temperature-holding kiln for combustion via a spray inlet, and adjust the mixed flow ratio of gas and air (about _ 1: 3 to 1: 1) to produce a Reduction flame. Control the inside of the kiln to a high-temperature reducing atmosphere (you can use the flame color observation to make judgment adjustments). After the battery has been treated for 1 hour at high temperature in the host kiln ^ from the bottom The bottom products released from the discharge port are mainly nickel: manganese, iron and other metals, and their mercury: cadmium. The arsenic content is less than 1.0 PP Μ, and zinc-rich and cadmium-rich are collected in each temperature-holding kiln. And bottom products of mercury? ---------- > Packing ------- 1T (Please read the precautions on the back before filling out this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 specification (210 × 297 public directors)