201013123 六、發明說明： 【發明所屬之技術領域】 本發明係與廢棄物焚化產生之有害飛灰技術領域 有關，更詳而言之是指一種含重金屬焚化飛灰之無金 化處理方法，其可將含重金屬之有害飛灰處理為無害 且可再利用之物質。 【先前技術】 參 廢棄物焚化產生之飛灰，經毒性特性溶出程序 (toxicity characteristic leaching procedure，TCLP)檢 測重金屬濃度，Pb常逾溶出毒性（leaehing t〇xichy) 法規標準（偶亦可能包括Cd )，故為有害事業廢棄物， 而無法逕行再利用。目前我國廢棄物焚化產生之有害 飛灰均以水泥（另亦多添加穩定劑）進行固化/穩定化 處理，再行獨立之衛生掩埋。惟，此法不僅增加廢棄 物體積、掩埋場容積、處理成本，且有害物質仍有再 ❹溶出之可能，實不符「資源化、減量化」等之廢棄物 處理原則。 習知有關廢棄物或其他物質焚化產生之飛灰（ ash)或/及底渣（bottom ash 〇r b〇tt〇jn residue)之相 關技術，如中華民國發明第2〇丨332號「從微粒物料中 提取礦物貴重金屬的方法及裝置」、第2〇1333號「從 微粒物料中提取礦物貴重金屬的方法及化學熱反應器 裝置」、第201334號「從微粒物料中提取礦物貴重金 4 201013123 屬的方法及氣力重力分離裝置」、第3〇1697號「灰燼 之穩定與再利用」、第393448號「使灰份轉變成惰性 之方法」、第468021號「灰熔融方法及灰熔融爐」、 第502099號「再加工垃圾熱處理之爐渣及/或灰爐之 方法」、第523550號「以電弧爐將垃圾焚灰 再利用之煉鋼方法」、第1278442號「除去底灰所含 氯化物之方法及系統」及公開第2〇〇52〇832號「廢棄 ，炅化衍生飛灰重金屬去除之方法」、第200740692 號「煤灰製成吸附材料之方法」、第2〇〇745495號「焚 化爐飛灰進料裝置」等專利案及公開案。 進一步探討前揭關於廢棄物或其他物質焚化產生 之飛灰或/及底渣之相關技術，其中，第3〇1697號專 例係將灰燼以800-960。(：焚化、酸浸、燒結、磨粉等 程序處理；第393448號專利係將含重金屬及鋁金屬灰 分加入磷酸及鹼金屬磷酸鹽，使成為灰漿後硬化；第 參 468021號專利係以高溫熔融灰；第5〇2〇99號專利係 將垃圾熱解成爐渣或/及灰燼，再以旋轉窯高溫氣化重 金屬；第523550號專利係在電弧爐之熔爐中加入飛灰 以處理飛灰；公開第200520832號「廢棄物焚化衍生 飛灰重金屬去除之方法」係本案發明人之另一申請專 利之技術’該方法係針對焚化廠内不同處所產生含不 同重金屬種類之原始飛灰及反應飛灰，將二者飛灰取 出以相反於相對濃度比例之數量混合，俾先行降低混 201013123 合飛灰之重金屬濃度’再藉4-8倍水洗方式去除飛灰 之重金屬。 由上可知，習知處理焚化產生之飛灰相關技術多 係採火法冶金（pyrometallurgy )、高溫熔融（meiting )、 氣化（gasification)、沉澱（precipitation )等方式， 其主要機制係將飛灰重金屬由固相轉為氣相之相轉移 (phase transformation )及固定化（immobilizati〇n )。 本案則主要採成本較低且可有效移出飛灰重金屬之萃 取（extraction)機制，亦為將飛灰重金屬由固相轉為 液相而移出之相轉移機制。 【發明内容】 ❹ 本發明主要目的係提供一種含重金屬焚化飛灰二 無害化處理方法，其完全依照焚化廠焚化後全部飛） j向進行處理（即原始飛灰與反應飛灰經由廠㈣ 送官道匯合後欲進入固化廠前之全部飛灰），可將i 部飛灰中有害重金屬加以去除並達到無害之目伊，々 處理後之無害飛灰能作為㈣用之原料，; 棄」、「資源再利用」之目的。 零肩 緣是，為達成前述之目的，本發明提供一 金屬焚化飛灰之無害化處理方法，至少包含以下 備取焚化飛灰及製備萃取^驟 產生之有害飛灰及製備所需卒::二取㈣ 第一階段萃取、固液分離處理：將萃取劑加入飛 6 201013123 灰中’使二者充分混合為飛灰泥漿並進行萃取，再將 萃取後之飛灰泥漿脫水’使飛灰與濾液分離，該萃取 劑係清水或弱鹼性溶液； 第二階段萃取、固液分離處理：將萃取劑加入經 第一階段萃取、固液分離後之飛灰中，使二者充分混 合為飛灰泥漿並進行萃取，再將萃取後之飛灰泥 水’使飛灰與濾液分離’該萃取劑係酸性溶液； 烘乾：將第二階段萃取、固液分離後之飛灰烘乾； 粉碎：將烘乾飛灰粉碎；及 檢測：檢測粉碎飛灰之TCLP溶出值，若及格， 則粉碎飛灰即為可再利用之無害物質；若未及格，則 重回第二階段萃取、固液分離處理之步驟。 【實施方式】 以下，兹舉本發明較佳實施例並配合圖式作詳細 之說明如後： 凊參閱各圖所示’本發明較佳實施例之含重金屬 焚化飛灰之無害化處理方法，主要包含下列步驟： 本發明之第一步驟係備取焚化產生之有害飛灰 $製備萃取劑100:有害飛灰為廢棄物焚化廠產生之 軋灰，以大型垃圾焚化廠而言，即是原始飛灰與反應 飛灰經由廠内輸送管道匯合後欲進入固化廠前之全部 飛灰萃取劑包括清水、弱驗液及中等濃度酸液。清 水為自來水、蒸餾水、或經軟水處理之水，弱鹼液為 201013123 浪度介於0.001至0.05 N之NaOH鹼液，中等濃度酸 液為派度介於0.5至2.0 Μ之h2S04或HN〇3酸液。 本發明之第二步驟係第一階段萃取、固液分離處 理110，包含有以下步驟： 混合萃取111 :將清水或弱鹼液加入飛灰中，利 用攪拌、振盪等方式將飛灰與清水或弱鹼液之萃取劑 充分混合，並進行萃取。「固（乾重）：液重量比」 _ 為1 : 2_3，轉速為100-250 rpm，時間為4—12小時， 俾有利於飛灰中重金屬與萃取劑充分接觸及反應，並 進行質量傳輸（mass transfer )機制之萃取。 浸潰萃取112 :將混合萃取之飛灰泥漿（slurry ) 靜置8-16小時進行浸潰萃取，即以時間讓飛灰顆粒内 之重金屬以擴散（diffusion)機制慢慢釋出。 固液分離113 :將經浸潰萃取之飛灰泥漿以壓 濾、真空過濾或離心等脫水方式，將飛灰與廢液分離。 0 本發明之第二步驟係第二階段萃取、固液分離處 理120 ’包含有以下步驟： 混合萃取121:將中等濃度酸液加入第一階段固 液分離後之飛灰（約含50%水分）中，利用攪拌、振 盪等方式將飛灰與中等濃度酸液之萃取劑充分混合， 並進行萃取。「固（濕重）：液重量比」為1 : 1一15， 轉速為100-250 rpm，時間為4_12小時，俾有利於飛 灰中重金屬與萃取劑充分接觸及反應，並進行質量傳 8 201013123 、 輸（mass transfer )機制之萃取。 次/貝萃取122 ·將混合萃取之飛灰泥漿靜置8— 小時進行浸潰萃取，即以時間讓飛灰顆粒内之重金屬 以擴散（diffusion)機制慢慢釋出。 固液分離123:將第二階段浸潰萃取之飛灰泥漿 以壓滤、真空過渡或離心等脫水方式，將飛灰與廢液 分離。 本發明之第四步驟係烘乾13〇:以l〇〇—2〇〇〇c之 溫度加熱烘乾第二階段固液分離後之飛灰，以去除飛 灰中之水分。 本發明之第五步驟係粉碎14〇:以粉碎機將供乾 後之飛灰粉碎，粉碎後飛灰粒徑應小於1 爪瓜。 本發明之最後步驟係檢測15〇 :檢測粉碎飛灰之 TCLP溶出值，若及格，驗碎飛灰即為可再利用之益 害物質；若未及格’則重回第二階段萃取、固液分離 =之步驟’直至⑽溶出值及袼為止。惟’混合 卒取121之步财「固（乾重）：液重量比」為1:2 一3。 出之：:匕第一及第二階段萃取、固液分離處理分離 出之3重金屬廢液應進入廢水處理廠進行處理。 相而2可知，本發明係將飛灰重金屬由固相轉為液 =乃其:僅處理後之飛灰均已無害，且處理成本 低乃甚具環保概念之創新方法。 綜上所述，本發明含重金屬焚化飛灰之無害化方 9 201013123 依照焚化廠焚化後全部飛灰之流向進行處 ’：將王部飛灰中有害重金屬加以去除並達到無害 之目標’俾處理後之無害飛灰能作為再利用之原料， 達到零廢棄」、「資源再利用」之目的；緣是，本 發明確實符合發明專利之要件，爰依法提出申請。 【圖式簡單說明】 圖一係本發明一較佳實施例之流程圖。 圖二係本發明一較佳實施例中第一（第二）階段 萃取、固液分離處理之流程圖。 【主要元件符號說明】 備取焚化產生之有害飛灰及製備萃取劑100 第一階段萃取、固液分離處理1 10 混合萃取111 浸潰萃取112 固液分離113 參 第二階段萃取、固液分離處理120 混合萃取121 浸潰萃取122 固液分離123 烘乾130 粉碎140 檢測150201013123 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the field of harmful fly ash technology generated by waste incineration, and more particularly to a gold-free treatment method for heavy metal incineration fly ash, Harmful fly ash containing heavy metals can be treated as a harmless and reusable substance. [Prior Art] The fly ash produced by waste incineration is tested for heavy metal concentration by toxicity characteristic leaching procedure (TCLP), and Pb often exceeds the leaehing t〇xichy regulatory standard (may include Cd) Therefore, it is a hazardous business waste and cannot be reused. At present, the harmful fly ash produced by waste incineration in China is solidified/stabilized by cement (and more stabilizers are added), and then it is buried in an independent sanitary burial. However, this method not only increases the volume of waste, the volume of landfill, and the cost of disposal, but also the possibility that the harmful substances will be dissolved again. This is inconsistent with the principle of waste disposal such as “resources and reductions”. Known technologies related to fly ash or bottom ash 〇 〇 〇 〇 〇 n n n 废弃物 废弃物 废弃物 , , , , , , , , , , , , , 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从Method and apparatus for extracting precious metals from minerals", No. 2, No. 1,133 "Method for extracting precious metals from particulate materials and chemical thermal reactor device", No. 201334 "Extracting mineral precious gold from particulate materials 4 201013123 genus Method and pneumatic gravity separation device", No. 3, 1697 "Stabilization and Reuse of Ash", No. 393448 "Method for Converting Ash to Inert", No. 468021 "Glass Melting Method and Ash Melting Furnace", No. 502099 "Method for reprocessing waste slag and/or ash furnace for waste heat treatment", No. 523550 "Steelmaking method for recycling waste ash in electric arc furnace", No. 1 278 844 "Removing chloride contained in bottom ash" Method and System" and Publication No. 2, No. 52, No. 832, "Methods for Removal of Heavy Metals from Degradation of Deuterated Fly Ash", No. 200740692 "Method for Adsorption of Admixed Materials from Coal Ash", No. 2, No. 745495 Means incinerators fly 'like the case of Patent publications and feed. Further explore the related technologies related to fly ash or/and bottom slag generated by incineration of waste or other substances. Among them, the special case No. 3, 1697 is to use ash as 800-960. (: incineration, acid leaching, sintering, milling, etc.; 393448 patent adds heavy metals and aluminum metal ash to phosphoric acid and alkali metal phosphate to make it hard to be mortar; Ref. 468021 patents are melted at high temperature Ash; No. 5〇2〇99 patent pyrolyzes waste into slag or/and ash, and then vaporizes heavy metals at a high temperature in a rotary kiln; Patent No. 523550 adds fly ash to a furnace of an electric arc furnace to treat fly ash; Publication No. 200520832, "Method for Removing Heavy Metals from Waste Incineration-Derived Fly Ash" is another patent application technology of the inventor of the present invention. This method is for producing raw fly ash and reaction fly ash containing different heavy metal species in different places in the incineration plant. Take the fly ash out and mix it in the opposite direction of the relative concentration ratio. Firstly, reduce the heavy metal concentration of the mixed 201013123 fly ash and then remove the heavy metal of the fly ash by 4-8 times washing. From the above, the conventional treatment Fly ash related technologies produced by incineration, multi-system pyrometallurgy, high-temperature melting, gasification, precipitation n) and other methods, the main mechanism is to transfer fly ash heavy metals from solid phase to gas phase phase transformation and immobilization (immobilizati〇n). This case is mainly low cost and can effectively remove fly ash heavy metals The extraction mechanism is also a phase transfer mechanism for transferring fly ash heavy metals from solid phase to liquid phase. SUMMARY OF THE INVENTION The main object of the present invention is to provide a harmless treatment method for heavy metal incineration fly ash. It is completely processed according to the incineration of the incineration plant. (ie, all the fly ash before the original fly ash and the reaction fly ash are sent to the curing plant after being sent to the official road through the factory (4)), which can be harmful in the fly ash of the i part. The heavy metal is removed and the harmless eye is achieved. The harmless fly ash after the treatment can be used as the raw material for (4), and the purpose of "recycling" and "recycling resources". The zero shoulder edge is, for the purpose of achieving the foregoing, the present invention provides a method for the harmless treatment of a metal incineration fly ash, comprising at least the following incinerated fly ash and the preparation of the extracted fly ash and the preparation of the required stroke: Second take (four) The first stage of extraction, solid-liquid separation treatment: the extractant is added to the fly 6 201013123 ash 'to make the two fully mixed into fly ash mud and extract, and then the extracted fly ash mud dehydrated' to make fly ash and The filtrate is separated, the extracting agent is a clean water or a weakly alkaline solution; the second stage of extraction, solid-liquid separation treatment: adding the extracting agent to the fly ash after the first stage extraction and solid-liquid separation, so that the two are fully mixed into a fly The mortar is extracted and the fly ash water is extracted to separate the fly ash from the filtrate. The extractant is an acidic solution; drying: drying the fly ash after the second stage extraction and solid-liquid separation; pulverizing: The dried fly ash is pulverized; and the test: the TCLP dissolution value of the crushed fly ash is detected. If it passes, the crushed fly ash is a harmless substance that can be reused; if it fails, the second stage extraction, solid-liquid separation is returned Li's steps. [Embodiment] Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the drawings as follows: 凊 Referring to the drawings, the harmless treatment method for heavy metal incineration fly ash according to the preferred embodiment of the present invention is The invention mainly comprises the following steps: The first step of the invention is to prepare the harmful fly ash produced by incineration. The extractant 100 is prepared: the harmful fly ash is the ash produced by the waste incineration plant, which is the original waste incineration plant. All fly ash extractants that are required to enter the solidification plant after the fly ash and the reaction fly ash have merged through the in-plant transfer pipeline include clean water, weak test liquid and medium concentration acid solution. The clean water is tap water, distilled water, or water treated with soft water. The weak alkali solution is 201013123 NaOH lye with a wave length of 0.001 to 0.05 N, and the medium concentration acid solution is h2S04 or HN 〇 3 with a degree of 0.5 to 2.0 Μ. Acid solution. The second step of the present invention is a first-stage extraction, solid-liquid separation treatment 110, comprising the following steps: Mixed extraction 111: adding fresh water or weak lye into the fly ash, using fly, ash or the like by stirring or shaking, or The extractant of the weak lye is thoroughly mixed and extracted. "Solid (dry weight): liquid weight ratio" _ is 1: 2_3, rotation speed is 100-250 rpm, time is 4-12 hours, 俾 is beneficial to the full contact and reaction of heavy metals in the fly ash with the extractant, and mass transfer (mass transfer) extraction of the mechanism. Immersion extraction 112: The mixed extracted fly syrup is allowed to stand for 8-16 hours for impregnation extraction, that is, the heavy metal in the fly ash particles is slowly released by a diffusion mechanism in time. Solid-liquid separation 113: The fly ash is separated from the waste liquid by dewatering of the fly ash slurry by impregnation and extraction by vacuum filtration, vacuum filtration or centrifugation. 0 The second step of the present invention is a second-stage extraction, solid-liquid separation treatment 120' comprising the following steps: Mixed extraction 121: adding a medium concentration acid solution to the fly ash after the first stage solid-liquid separation (about 50% moisture) In the method, the fly ash is thoroughly mixed with the medium concentration acid extractant by stirring, shaking, or the like, and extracted. "Solid (wet weight): liquid weight ratio" is 1: 1-15, the speed is 100-250 rpm, the time is 4_12 hours, which is beneficial to the full contact and reaction of heavy metals in the fly ash with the extractant, and the quality is transmitted. 201013123, the extraction of the mass transfer mechanism. Sub/Bei extraction 122. The mixed extraction of the fly ash slurry is allowed to stand for 8 hours for the impregnation extraction, that is, the heavy metal in the fly ash particles is slowly released by a diffusion mechanism in time. Solid-liquid separation 123: The fly ash of the second stage impregnation extraction is separated from the waste liquid by dewatering by pressure filtration, vacuum transfer or centrifugation. The fourth step of the present invention is to dry 13 〇: heating and drying the fly ash after the second stage solid-liquid separation at a temperature of l〇〇-2〇〇〇c to remove moisture in the fly ash. The fifth step of the present invention is to pulverize 14 〇: the fly ash after being dried is pulverized by a pulverizer, and the particle size of the fly ash after pulverization should be less than 1 claw melon. The final step of the invention is to detect 15 〇: detecting the TCLP dissolution value of the crushed fly ash. If it passes, the crushed fly ash is a reusable beneficial substance; if it fails, it returns to the second stage extraction, solid-liquid The step of separation = 'up to (10) the dissolution value and enthalpy. However, the "solid (dry weight): liquid weight ratio" of the mixed stroke of 121 is 1:2 to 3. The following:: The first and second stage extraction and solid-liquid separation and separation of the three heavy metal waste liquid should be treated in the wastewater treatment plant. It can be seen that the present invention converts fly ash heavy metals from solid phase to liquid = it is: only the treated fly ash is harmless, and the low processing cost is an innovative method with environmental protection concept. In summary, the harmless chemical layer containing heavy metal incineration fly ash according to the present invention 9 201013123 is carried out according to the flow of all fly ash after incineration of the incineration plant': removing harmful heavy metals from the fly ash of Wangbu and achieving the goal of harmlessness 俾 treatment The latter harmless fly ash can be used as a raw material for reuse, achieving the purpose of zero waste and "recycling of resources". The reason is that the present invention does meet the requirements of the invention patent and submits an application according to law. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of a preferred embodiment of the present invention. Figure 2 is a flow chart showing the first (second) stage extraction and solid-liquid separation treatment in a preferred embodiment of the present invention. [Explanation of main component symbols] Prepare harmful fly ash from incineration and prepare extractant 100 First stage extraction, solid-liquid separation treatment 1 10 Mixed extraction 111 Immersion extraction 112 Solid-liquid separation 113 Reference second stage extraction, solid-liquid separation Treatment 120 Mixed extraction 121 Immersion extraction 122 Solid-liquid separation 123 Drying 130 Crushing 140 Testing 150