| 台灣地區經由焚化處理所產生之飛灰數量龐大，且經毒性特性溶出試驗(TCLP)之判定為有 |
| 害事業廢棄物，故無法直接掩埋或再利用。目前焚化飛灰之處理多採固化法，但固化體長 |
| 期穩定性堪慮，有二次污染之虞。然熱處理法之熔渣穩定性高，但大部份之重金屬氯化物 |
| 極易蒸發，有先行蒸發形成廢氣之虞，實難斷言重金屬封存於融渣之中，因此本研究預計 |
| 於熱處理程序中設計廢氣收集採樣設備，收集熱處理中之蒸發廢氣，並比較水萃前處理對 |
| 熱處理時重金屬分佈狀況之影響。 |
| 本研究基於飛灰種類及特性之不同，將細分為集塵灰及反應灰，再以不同溫度及時間予以 |
| 熱處理，以探討其重金屬於熱處理程序中之分佈，並進行氣固相之質量平衡分析以確保實 |
| 驗之可信度。而集塵灰於實驗中可發現，其性質良好並不需任何前處理即可達熔融狀態， |
| 不若反應灰之熔點過高，不利於熱處理，因此，本研究以水萃為前處理，將反應灰中可溶 |
| 性之鈣與鹽類萃除，除降低其熔點外，亦減少鹽類之干擾，並減少在處理程序中形成金屬 |
| 氯化物之機會。同時，藉由動力方程式求其反應速率常數，以瞭解重金屬蒸發之速率。 |
| 本研究共探討四種重金屬Pb、Zn、Cu、Cd之熱處理蒸發特性，由實驗結果顯示，當集塵灰 |
| 及水萃反應灰達熔融狀態時，Pb為最易蒸發之金屬，其蒸發率皆達99 %，且反應速率最快 |
| ；Cd之蒸發率亦高達90 %；而 Cu之蒸發率則為80 %；Zn為熱處理程序中較難蒸發之物種， |
| 但亦有57 %之蒸發率。就整體而言，該四種金屬於熱處理程序中，皆已大量蒸發至氣相， |
| 由此可證明當飛灰於熱處理程序時，其重金屬並未封存於熔渣當中，反而是蒸發成氣態逸 |
| 散，而造成熱處理時之二次污染。 |
|
| [摘要] |
| The incineration process of municipal solid waste will accompanies a large |
| number of fly ashes, and the TCLP (Toxicity Characteristic Leaching Procedure) |
| shows it is hazardous waste, which can’t be treated by landfill or reuse |
| directly. Solidification is used to apply in the fly ashes handling, but the |
| product is still unstable. Thermal treatment methods are the most popular |
| alternatives in many countries; however, the most metallic chlorides are |
| easily to evaporate through the flue gas. In this study, flue gas is |
| collected, and discuss by the mass balance analysis to discover the behavior |
| of heavy metals during the thermal treatment process of MSWI fly ash. The |
| washing of the fly ash was also executed before the thermal treatment as a |
| comparison, in order to lower down the harmful calcium ion and chloride. |
| The fly ash samples were collected from the cyclone and bag-house blow downs |
| separately in a MSWI, the different temperature and retention time were |
| designed in the experiments to simulate the melting condition. A tube furnace |
| was adopted, the behavior of Pb, Zn, Cu and Cd were analyzed. The results show |
| that the cyclone ash is easy to melt without pre-washing, but the reacted ash |
| is difficult to reach its melting point. For this reason washing pretreatment |
| was used to extract Ca and Cl in order to decrease the melting point. |
| The results showed that, when the cyclone ashes and pre-washed reaction ashes |
| reached their melting point, Pb is the most easily to evaporate, the |
| evaporation ratio reached 99 %, and the reaction rate is also the fast one. |
| The evaporation ratio of Cd, Cu and Zn are 90 %, 80 % and 57%, respectively. |
| The most portion of the heavy metals are evaporated accompany with the flue |
| gas during the thermal treatment operation, it is not stabilized in the slag; |
| it should be pays much attention during the thermal treatment process. |
|
| [論文目次] |
| 一、前言 |
| 1-1研究源起 1 |
| 1-2 研究目的 2 |
| 二、文獻回顧 |
| 2-1焚化飛灰種類及來源 3 |
| 2-2 垃圾焚化飛灰性質 |
| 2-2-1 物理性質 4 |
| 2-2-2 化學性質 5 |
| 2-3.垃圾焚化飛灰中重金屬來源及特性 |
| 2-3-1 焚化飛灰中重金屬來源 10 |
| 2-3-2飛灰中重金屬之生成機制 11 |
| 2-4 焚化飛灰熱處理法 13 |
| 2-5熱處理法於固體廢棄物上之應用 |
| 2-5-1 燒結於資源化之應用 15 |
| 2-5-2 熔融於固體廢棄物之應用 16 |
| 2-6 熱處理法之之二次污染特性 19 |
| 三、研究方法、設備與流程 |
| 3-1 實驗材料 26 |
| 3-1-1都市垃圾焚化飛灰 24 |
| 3-1-2實驗藥品及器材 25 |
| 3-1-3實驗及分析設備 26 |
| 3-2實驗設備 28 |
| 3-3 實驗流程 30 |
| 3-4實驗方法 |
| 3-4-1樣品前處理 31 |
| 3-4-2 垃圾焚化飛灰之基本檢測項目 31 |
| 3-4-3 飛灰熔融過程中重金屬釋出之研究 34 |
| 3-4-4 水溶性物質對重金屬分布之影響 35 |
| 四、結果與討論 |
| 4-1飛灰之基本性質比較分析 |
| 4-1-1 粒徑分析 37 |
| 4-1-2灼燒減量及pH值 39 |
| 4-1-3主要成分分析 39 |
| 4-1-4重金屬全量分析 40 |
| 4-1-5毒性特性溶出實驗 42 |
| 4-2集塵灰於熱程序中之重金屬分佈狀況 |
| 4-2-1 停留時間對重金屬分佈之影響 43 |
| 4-2-2集塵灰中重金屬蒸發之反應速率 47 |
| 4-2-3操作溫度對重金屬分布之影響 50 |
| 4-2-4爐內氣氛對重金屬分布之影響 53 |
| 4-3反應灰於熔融程序中之重金屬分布狀況 |
| 4-3-1操作溫度對重金屬分布之影響 56 |
| 4-3-2反應灰水萃處理各元素之溶出率及質量平衡 57 |
| 4-3-3水萃前後之物種組成型態 59 |
| 4-4水萃反應灰於熱處理程序中之重金屬分布狀況 |
| 4-4-1停留時間對重金屬分佈之影響 62 |
| 4-4-2水萃反應灰中重金屬蒸發之反應速率 66 |
| 4-4-3操作溫度對重金屬分布之影響 68 |
| 4-4-4爐內氣氛對重金屬分布之影響 71 |
| 4-5 重金屬蒸發特性之綜合討論 |
| 4-5-1 Pb之蒸發特性 73 |
| 4-5-2 Zn之蒸發特性 73 |
| 4-5-3 Cu之蒸發特性 76 |
| 4-5-4 Cd之蒸發特性 76 |
| 五、結論與建議 |
| 5-1結論 77 |
| 5-2建議 79 |
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