砍、發明_明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說 明） 本發明係與廢棄物處理有關，特別是關於一種以重金 屬物種轉化、燒結、瓷化合併處理含重金屬廢棄物之方法。 習知危害性廢棄物（hazardous waste)處理方法，包含有 化學穩定及固化（Chemical Stabilization/ Fixation)、匣限法 5 (Encapsulation)、接毒法（Detoxification)等；但上述處理法 均有其缺陷存在，且大多不易通過或僅免強通過我國環保 署所公告「毒性特性溶出試驗」（Toxicity Characteristics Leachablity Procedure, TCLP)的檢測；而處理後之廢棄物 大多無法再利用，需要經過掩埋的動作，而這些廢棄物所 10 造成的長期性渗出（leaching)或去固化勢（defixation potentials)等現象，此等二次污染問題對環境的所造成影響 是無法估計的。 以往對於含重金屬廢棄物的處理方式大多是採用固化 法’其方式為：將前述之廢棄物混合水泥與螯化劑等化學 15固化劑，使其固化成固體，最後再經過掩埋的處理步驟。 但經過長時間後，該處理後之固體會逐漸崩解，而令包含 在其中的毒性物質逸出。亦即，習知的用固化法處理含重 金屬廢棄物，無法避免長期滲出以及去固化勢等會造成二 次污染的問題。日前台塑的汞污泥事件即為一最佳事證。 20 本發明之主要目的在於提供一種以重金屬物種轉化、 燒結、瓷化合併處理含重金屬廢棄物之方法，可有效降低 危害性廢棄物的毒性。 本發明之又一目的在於提供一種以重金屬物種轉化、 燒結、瓷化合併處理含重金屬廢棄物之方法，經過本發明 0續次頁（發明說明頁不敷使用時，請註記並_續頁）Chop, invention _ Ming (the description of the invention should state: the technical field to which the invention belongs, the prior art, content, embodiments and drawings are briefly explained) The present invention is related to waste treatment, especially about a heavy metal species transformation and sintering 3. Porcelainization combined treatment method for heavy metal waste. Conventional hazardous waste treatment methods include Chemical Stabilization / Fixation, Encapsulation 5 and Detoxification, etc .; however, the above treatment methods have their defects. Existence, and most of them are not easy to pass or are only exempted from passing the test of "Toxicity Characteristics Leachablity Procedure (TCLP)" announced by the Environmental Protection Agency of China; and most of the treated waste cannot be reused and needs to be buried. The long-term leaching or depotation potentials caused by these wastes10, the impact of these secondary pollution problems on the environment cannot be estimated. In the past, most of the treatment methods for heavy metal-containing wastes were by solidification method. The method was to mix the aforementioned waste with cement and chelating agents such as chemical 15 curing agents to solidify them, and then go through the landfill treatment step. However, after a long period of time, the treated solid will gradually disintegrate, and the toxic substances contained therein will escape. That is, the conventional solidification method for the treatment of heavy metal-containing waste cannot avoid the problems of secondary pollution such as long-term leaching and desolidification. The best example is the mercury sludge incident at the front desk. 20 The main object of the present invention is to provide a method for treating heavy metal-containing waste by transforming, sintering, and porcelainizing heavy metal species, which can effectively reduce the toxicity of hazardous waste. Yet another object of the present invention is to provide a method for treating heavy metal waste by combining heavy metal species transformation, sintering, and porcelainification. After the present invention, the next page (if the description page of the invention is insufficient, please note and continue _ continued page)
處搜後之廢棄物， 可再利用於其他用途。 為達成上述目的，依據本發明所提供之含重金屬廢棄 2處埋法，係利用含重金屬污泥充分混合黏土，再經過高 =蜞烤，使混合物在高溫環境下，各種物質重新键結或部 辦鐽，以改變重金屬或氰化物等有毒物質的化學性質， 而達到無害化，甚至資源化。 瓷化反應為本發明之重要原理，在高溫下，污泥中之 重金屬將與黏土中之氧化矽及氧化鋁等成分結合，進行重 新鍵結，或使重金屬原子拘限於黏土的矽化物（silieate)與 10 招化物（aluminate)等分子結構中。而經資化反應後之產物， 其強度類似石石，比市售碑而，可供建材或環境工程中廢 水處理的生物接觸滤材等用途使用。 另一原理為高溫氧化，例如在高溫下，劇毒性的氰化 物（CN_)會分解為無毒之二氧化碳(C〇2)以及氮氣(n2：^而 15高毒性之六價鉻(Cr6+)也會轉變為三價鉻(Cr3,。 以下茲舉一較佳實施例對本發明作進一步之說明： 本發明實施例所處理之廢棄物，為某電鍍廠所產出之 污泥，該污泥經脫水機脫水後其含水量為78%，其中所包 含主要之重金屬成分，如鉻(Cr)以及鋅（Zn)之TCLP溶出 20 量分別為259,000 mg/L與2,580 mg/L;其他如採樣時間、 地點與污泥中其他各類重金屬和毒性物質的含量，以及檢 測方法如附件一所示。在附件一中的數據顯示：原污泥中 各類重金屬以及氰化物之TCLP檢測值均遠高於環保署公 告之「溶出毒性事業廢棄物溶出試驗標準」。 -4· 593199The recovered waste can be reused for other purposes. In order to achieve the above purpose, according to the two buried methods of heavy metal-containing waste provided by the present invention, clay is thoroughly mixed with heavy metal-containing sludge, and then subjected to high = roasting, so that the mixture is rebonded or separated under high temperature environment. It is necessary to change the chemical properties of toxic substances such as heavy metals or cyanide to achieve harmlessness and even resource utilization. Porcelaination is an important principle of the present invention. At high temperatures, heavy metals in sludge will be combined with components such as silica and alumina in clay for re-bonding, or heavy metal atoms will be confined to the silicide of clay. ) And 10 molecular compounds (aluminate). The strength of the product after the capitalization reaction is similar to that of stone. It can be used for building materials or biological contact filter materials for waste water treatment in environmental engineering. Another principle is high-temperature oxidation. For example, at high temperatures, highly toxic cyanide (CN_) will decompose into non-toxic carbon dioxide (C02) and nitrogen (n2: ^ and 15 highly toxic hexavalent chromium (Cr6 +)). Transformed into trivalent chromium (Cr3 ,.) The following is a further description of the present invention by a preferred embodiment: The waste treated in the embodiment of the present invention is sludge produced by a certain electroplating plant, and the sludge is dehydrated After dehydration, the water content is 78%, and the major heavy metal components, such as chromium (Cr) and zinc (Zn) TCLP dissolution 20 are 259,000 mg / L and 2,580 mg / L; others such as sampling time, The content of other types of heavy metals and toxic substances in the site and sludge, and the detection methods are shown in Annex 1. The data in Annex I shows that the TCLP detection values of various heavy metals and cyanide in the original sludge are much higher than "Dissolution Test Standard for Dissolution of Toxic Business Waste" announced by the Environmental Protection Agency. -4 · 593199
本發明之處理步驟為，首先將該污泥先經預定時間烘 烤，以除去該污泥中之水分；再加入約1.5倍重的黏土以 及約5%之安定劑（如含二價鐵(Fe2+)之無機化合物），其作 用在於助熔以及加速拘限污泥中之重金屬成分；為了使其 5 充分混合，因此必須再經過研磨、攪拌等動作；之後加入 預定比例的水，加壓以製成預定形狀之混合物，以使處理 後之產物可直接再利用。The treatment step of the present invention is: firstly baking the sludge for a predetermined time to remove the moisture in the sludge; then adding about 1.5 times the weight of clay and about 5% of a stabilizer (such as containing divalent iron ( Fe2 +) inorganic compound), its role is to promote melting and accelerate the restriction of heavy metal components in sludge; in order to make it fully mixed, it must be ground, stirred and other actions; then add a predetermined proportion of water, pressurized to The mixture is made into a predetermined shape so that the processed product can be directly reused.
接著將上述混合物送入一烘烤爐中加熱，其加熱時間 當視污泥混合物之總量及所含重金屬成份及濃度而定；而 10 加熱的方式則採階段式加熱法，其中第一階段之加熱溫度 約為105°C左右，其目的在於去除水分；第二階段之加熱 溫度約為300°C左右，目的在於除去混合物中之結晶水; 第三階段之加熱溫度約為600°C左右，目的在於除去有機 物，並使混合物中各分子的鍵結初步重新組合；而第四階 15 段之加熱溫度約為800°C左右，目的在於使混合物中各分 子的鍵結再次重新組合，以達再利用之目的；各加熱階段 大約需維持20分鐘以上。最後加熱至1300t，使混合物 内之各成分在加熱的過程中充分進行瓷化以及高溫氧化等 燒結反應。 20 各加熱階段中之反應詳述如后： 1. 第一階段加熱至l〇5°C，亦即為超過水之沸點，其 目的在於去除污泥中大部分之水分。 2. 第二階段加熱至300°C左右，是為去除混合物中之 結晶水、附著水、吸附水等；重金屬化合物則會隨著分子 593199Then the above mixture is sent to a baking furnace for heating. The heating time depends on the total amount of the sludge mixture and the heavy metal content and concentration. The 10 heating method is a stage heating method, of which the first stage The heating temperature is about 105 ° C, the purpose is to remove moisture; the heating temperature in the second stage is about 300 ° C, the purpose is to remove the crystal water in the mixture; the heating temperature in the third stage is about 600 ° C , The purpose is to remove the organic matter, and make the bonding of the molecules in the mixture initially recombined; and the heating temperature of the 15th stage of the fourth stage is about 800 ° C, the purpose is to recombine the bonds of the molecules in the mixture again to To achieve the purpose of reuse; each heating stage needs to be maintained for more than 20 minutes. Finally, it is heated to 1300t, so that the components in the mixture fully undergo sintering reactions such as porcelainification and high temperature oxidation during the heating process. 20 The reactions in each heating stage are detailed as follows: 1. The first stage is heated to 105 ° C, which is beyond the boiling point of water, and its purpose is to remove most of the moisture in the sludge. 2. The second stage is heated to about 300 ° C in order to remove crystal water, adhered water, adsorbed water, etc. from the mixture; heavy metal compounds will follow the molecule 593199
鍵結開始重新組合，而開始物種轉化，使逐漸安定化。 3.第三階段加熱至600°C左右，是為去除大部分之有 機物，增加重金屬物種轉化速率，使之不易溶出，並減少 氣化傾向。 5 4.第四階段加熱至800°C左右，可使： 1) 重金屬繼續進行物種轉化； 2) 轉化後之重金屬與污泥、土壤、廢棄物等基質、 添力π劑、黏土逐漸反應究化反應，使重金屬不 易氣化與不易溶出，以及 10 3)污泥、土壤、廢棄物等基質、添加劑、黏土等 亦同時進行燒結反應，藉以形成細緻化結構， 圍阻重金屬。 5.最後再加熱至1300°C〜1400°C左右，使燒結、瓷化 反應更為徹底，甚或進行融熔反應。此階段之加熱溫度， 15 當視基質各成分比例而定，原則上大概需超過1000°C， 而加熱時間亦是因成分不同而有所差異。 待加熱完畢，將冷卻後之混合物取出，燒結後產物之 強度類似岩石，可作為人行道碑或其他種類之建材，或環 境工程中廢水處理的生物接觸濾材。 20 附件二為經本發明實施例各處理步驟處理後，其產物 之TCLP溶出液中各類重金屬及毒性物質含量的檢測報 告。其檢測結果顯示：各類重金屬以及氰化物之TCLP檢 測值均遠低於環保署公告之「溶出毒性事業廢棄物溶出試 驗標準」；尤其如鉛、銅、鉻以及氰化物之檢測值更是低 -6·The bonds begin to recombine, and species transformation begins, gradually stabilizing. 3. The third stage of heating to about 600 ° C is to remove most of the organic matter, increase the conversion rate of heavy metal species, make it difficult to dissolve, and reduce the tendency of gasification. 5 4. The fourth stage is heated to about 800 ° C, which can: 1) continue the species transformation of heavy metals; 2) the transformed heavy metals and the substrates such as sludge, soil, waste, etc., gradually react 3) The substrate, additives, clay, etc. of sludge, soil, waste, etc. also undergo sintering reaction at the same time to form a refined structure to contain heavy metals. 5. Finally, reheat to about 1300 ° C ~ 1400 ° C to make the sintering and porcelainization reaction more thorough, or even carry out the melting reaction. The heating temperature at this stage, 15 depends on the proportion of each component of the substrate. In principle, it needs to exceed 1000 ° C, and the heating time varies with different components. After the heating is completed, the cooled mixture is taken out. The strength of the sintered product is similar to that of rock. It can be used as a sidewalk monument or other types of building materials, or a biological contact filter material for wastewater treatment in environmental engineering. 20 Attachment II is a test report of the contents of various heavy metals and toxic substances in the TCLP eluate of the product after the treatment steps in the examples of the present invention. The test results show that the TCLP test values of various heavy metals and cyanide are far lower than the "dissolution test standards for dissolution of toxic business waste" announced by the Environmental Protection Agency; especially the test values of lead, copper, chromium, and cyanide are even lower. -6 ·
於方法偵測極限，顯示本發明之含重金屬廢棄物處理法具 有卓越之處理效果；此外，經本處理法處理後之產物可直 接再利用，可避免因掩埋所造成二次污染的可能，實具有 環保之功效。 以下二點為發明人提出，以本案所揭之方法處理重金 屬廢棄物應注意之事項： 1·對於某些高揮發性的重金屬，例如汞或坤，由於 其可能在階段加熱時，混合物產生燒結、瓷化反應前即揮 發。因此，對於具有高含量汞或坤的重金屬污泥，可能不 適用於本案所揭之處理方法，或是必須先用其他方式，預 先去除污泥内之汞或神。 2·階段加熱的過程中，大部分的重金屬均因燒結或 堯化而形成十分安定與不易揮發之狀態，其氣化逸出者十 分有限’縱然有少部分的重金屬因氣化而逸出，此時可以 濾袋或是洗滌的方式捕集，並將其送反至污泥混合處，再 次與黏土、安定劑等混合，而再次燒結、瓷化。The detection limit of the method shows that the heavy metal-containing waste treatment method of the present invention has an excellent treatment effect. In addition, the product treated by the treatment method can be directly reused, which can avoid the possibility of secondary pollution caused by landfill. Environmental protection. The following two points are proposed by the inventors to pay attention to the treatment of heavy metal waste by the method disclosed in this case: 1. For some highly volatile heavy metals, such as mercury or kun, the mixture may sinter when it is heated in stages 3. It is volatilized before the porcelain reaction. Therefore, for heavy metal sludge with a high content of mercury or kun, it may not be suitable for the treatment method disclosed in this case, or other methods must be used to remove mercury or spirit from the sludge in advance. 2. During the stage heating, most of the heavy metals are formed into a very stable and non-volatile state due to sintering or melting. The gasification escapers are very limited. 'Even if a small amount of heavy metals escapes due to gasification, At this time, it can be collected in a filter bag or washing method, and sent back to the sludge mixing place, mixed with clay, stabilizer, etc. again, and sintered and porcelainized again.