都市垃圾焚化飛灰是一種性質複雜，不易處理之有害廢棄物，目前台灣地區對都市垃圾焚化飛灰處理方式多採固化程序進行最終處置，但固化後體積增大，且重金屬有再溶出之疑慮，因此穩定飛灰中有害物質及進行再利用處理技術為未來趨勢。
  本研究主要探討濕式研磨對水洗後飛灰粉體之影響，分別使用粒徑分析儀、X-ray粉末繞射儀、掃描式電子顯微鏡等儀器，來分析粉體研磨前後之性質差異與變化，並且使用毒性特性溶出程序與序列萃取兩種實驗方法，來了解重金屬鉛隨研磨時間的溶出量與型態變化，以利於粉體後續之使用及研究方向。
  由實驗結果得知，飛灰經由水洗後，可以降低飛灰中氯鹽含量及重金屬鉛溶出量，然後藉由粒徑分析儀、SEM、XRD等分析探討濕式研磨後之粉體，找出最佳磨球比例為1：1、礦漿濃度10%、磨罐轉速93rpm、研磨液乙醇，而研磨後粉體性質除了縮減粉體粒徑外，從SEM觀察發現微米粒子是由更小之細微顆粒所組成，晶相物種波峰強度則會隨著研磨時間減弱，並再次降低重金屬鉛TCLP溶出濃度且符合法規值，因此研磨對於鉛TCLP溶出有穩定之效果，後續研究使用磷酸為研磨液，從序列萃取結果發現磷酸可以使鉛型態趨於穩定不溶出，同時讓研磨液鉛濃度與粉體中鉛溶出量均符合法規標準，確實達到穩定化效果。

Municipal solid waste incinerator (MSWI) fly ash is defined as hazardous waste, which is difficult to be handled due to its complicate composition. At present, all of them are treated by solidification/stabilization and then landfill in Taiwan. But the specimen occupied the landfill site and the heavy metals re-leaching in long-term still are the problems. Ball milling to super-fine particle could enhance the chemical reaction in the treatment, applying it on the stabilization of the heavy metals in fly ash, is anticipative to promote the opportunity of recovery and reusing.
  The study is to research the characteristic of water extracted fly ash followed by wet ball milling. By using of Particle Size Analyzer, X-ray Diffraction, Scanning Electron Microscope to identify the property of fly ash, then use toxicity characteristic leaching process (TCLP) and sequential extraction procedure (SEP) to analyze the leaching characteristics and bonding pattern of heavy metals.
  The results showed that, water-extraction could effectively reduce the chloride content, and leaching potential of Pb in fly ash. The optimum grinding condition in the experiment is：solid of slurry by weight is 10 %, rotation rate of milling jar is 93 rpm, and the milling dispersion solution is alcohol, the mixing ratio of milling media is 1:1(diameter of milling media is 5 and 15 mm respectively). After milled, particle size of water-extracted fly ash reduced gradually to micrometer grade detected by Ultra Particle Analyzer, but based on SEM observations, these micro-particles actually composed of smaller motes. The peak intensity of XRD decreased as increasing of milling time. In addition, leaching potential of Pb could be reduced to fit TCLP regulation after milling operation; it proved that the milling operation has the ability to stabilize Pb in fly ash. Appling phosphoric acid solution as the milling fluid and analyzing the product by SEP, the results showed that Pb can be stabilize as hard-to-leaching bounding type.

目錄
中文提要………………………………………………………………..Ⅰ
英文提要………………………………………………………………..Ⅱ
目錄 ……………………………………………………………………Ⅳ
圖目錄…………………………………………………………………..Ⅷ
表目錄………………………………………………………………...XI
第一章 序論
1-1 研究緣起…………………………………………………………..1
1-2 研究目的…………………………………………………………..2

第二章 文獻回顧
2-1 焚化飛灰來源及特性……………………………………………..3
2-1-1 焚化飛灰物理性質…………………………………………...4
2-1-2 焚化飛灰化學性質…………………………………………...5
2-1-3 焚化飛灰中重金屬來源與特性……………………………...6
2-2 水萃相關文獻……………………………………………………..9
2-3 超細粉體技術……………………………………………………10
2-3-1 粉碎理論…………………………………………………….10
2-3-2 超細粉體特性……………………………………………….12
2-4 研磨相關之研究………………………………………………...14
2-5 重金屬鍵結型態探討……………………………………………..16
2-6 以磷酸處理重金屬之相關研究…………………………………..18
第三章 實驗材料、設備與研究方法
3-1 實驗材料…………………………………………………………20
3-2 實驗藥品及器材…………………………………………………21
3-3 實驗設備…………………………………………………………22
3-4 分析設備…………………………………………………………24
3-5 研究方法…………………………………………………………26
3-5-1 研究流程圖………………………………………………….26
3-5-2 實驗方法…………………………………………………….27
3-5-3 水萃前處理操作條件……………………………………….34
3-5-4 研磨處理操作條件………………………………………….34
3-5-5 研磨後粉體之各項分析…………………………………….37
3-6 實驗配置…………………………………………………………...39
第四章 結果與討論
4-1 飛灰物理特性分析………………………………………………40
4-1-1 pH值、含水率及灼燒減量……………………………………40
4-1-2 粒徑分析……………………………………………………...41
4-1-3 SEM分析………………………………………………………42
4-2 飛灰化學特性分析………………………………………………44
4-2-1 元素分析……………………………………………………...44
4-2-2 晶相物種……………………………………………………...46
4-2-3 TCLP溶出濃度.…………………………………………...47
4-3 多段水萃對飛灰之影響…………………………………………49
4-3-1 多段水萃後水萃廢液氯離子含量分析…………………….49
4-3-2 多段水萃後水萃廢液pH、導電度變化……………………….50
4-3-3 多段水萃後水萃廢液重金屬含量分析…………………….51
4-4 水洗灰特性分析…………………………………………………52
4-4-1 水洗灰粒徑分析……………………………………………...52
4-4-2 水洗灰SEM 觀察……………………………………………..53
4-4-3 水洗灰元素分析……………………………………………...54
4-4-4 水洗灰XRD物種分析………………………………………..55
4-4-5 水洗灰毒性特性溶出程序…………………………………...56
4-5 研磨灰特性分析…………………………………………………57
4-5-1 研磨灰粒徑分析……………………………………………...57
4-5-2 研磨灰SEM分析…………………………………………….60
4-5-3 研磨灰XRD晶相物種分析.………………………………..66
4-5-4 研磨灰TCLP溶出濃度……………..……………………...69
4-5-5 研磨灰序列萃取……………………………………………...69
4-5-6 研磨灰比表面積……………………………………………71
4-6 研磨添加PbO水洗灰之分析…………………………………..72
4-6-1 添加PbO水洗灰重金屬溶出情形…………………………...72
4-6-2 添加PbO水洗灰晶相物種…………………………………...73
4-6-3 添加PbO水洗灰之序列萃取………………………………...75
4-7 使用磷酸研磨添加PbO水洗灰之分析…………………………77
4-7-1 使用磷酸研磨添加PbO水洗灰之重金屬溶出情形………...77
4-7-2 使用磷酸研磨添加PbO水洗灰晶相物種……..…………..79
4-7-3 使用磷酸研磨添加PbO水洗灰之序列萃取………………..81
第五章 結論與建議
  5-1 結論……………………………………………………………...83
  5-2 建議……………………………………………………………...85
參考文獻………………………………………………………………..86
附錄A  實驗數據……………………………………………………91
 
圖目錄
圖2-1 飛灰粒徑分佈特性……………………………………………....4
圖3-1 桌上型球磨機…………………………………………………..22
圖3-2 實驗流程圖……………………………………………………..26
圖3-3 序列萃取實驗方法與步驟……………………………………..33
圖3-4 磨球滾動轉速過慢……..………………………………………36
圖3-5 磨球滾動轉動過快…………..…………………………………36
圖3-6 磨球滾動之臨界轉速 ……….…………………………………37
圖4-1 反應灰粒徑分佈圖……………………………………………..41
圖4-2 鍋爐粒徑分佈圖………………………………………………..42
圖4-3 鍋爐灰SEM圖…………………………………………………43
圖4-4 反應灰SEM圖…………………………………………………43
圖4-5 反應灰XRD晶相物種分析……………………………………46
圖4-6 鍋爐灰XRD晶相物種分析……………………………………47
圖4-7 飛灰多段水萃後水萃廢液氯離子含量變化………………......49
圖4-8 飛灰多段水萃後水萃廢液pH值變化…………………………50
圖4-9 飛灰多段水萃後水萃廢液導電度變化………………………..50
圖4-10 飛灰多段水萃後水萃廢液重金屬含量變化............................51
圖4-11 水洗灰粒徑分佈圖……………………………………………52
圖4-12 水洗灰SEM圖……………………………………………….53
圖4-13 水洗灰XRD晶相物種分析………………….………………55
圖4-14 以乙醇當研磨液之粒徑變化圖………………………………59
圖4-15 以水當研磨液之粒徑變化圖…………………………………59
圖4-16 研磨液為乙醇之飛灰研磨24小時之SEM圖(1萬倍).……62
圖4-17 研磨液為乙醇之飛灰研磨96小時之SEM圖(1萬倍)….…62
圖4-18 研磨液為水之飛灰研磨24小時之SEM圖(1萬倍)………..63
圖4-19 研磨液為水之飛灰研磨96小時之SEM圖(1萬倍)…..……63
圖4-20 研磨液為乙醇之飛灰研磨96小時之SEM圖(5萬倍)…..…65
圖4-21 研磨液為水之飛灰研磨96小時之SEM圖(5萬倍).….……65
圖4-22 以乙醇為研磨液之XRD圖…………………………………..68
圖4-23 以水為研磨液之XRD圖……………………………...……..68
圖4-24 研磨液乙醇重金屬鉛隨研磨時間之型態變化………………70
圖4-25 研磨液水重金屬鉛隨研磨時間之型態變化…………………70
圖4-26 研磨灰比表面積隨研磨時間變化圖…………………………71
圖4-27 添加PbO研磨液中重金屬鉛溶出情況….………..…………72
圖4-28 添加PbO以乙醇研磨後XRD圖………………...…………..74
圖4-29 添加PbO以水研磨後XRD圖………………………………..74
圖4-30 添加PbO以乙醇研磨後鉛之型態變化………………………75
圖 4-31 添加PbO以水研磨後鉛之型態變化……..………………..76
圖4-32 使用磷酸研磨液中重金屬鉛溶出情況………….……....…78
圖4-33 使用低濃度磷酸溶液研磨後XRD圖….…….……………..80
圖4-34 使用高濃度磷酸溶液研磨後XRD圖………………………80
圖4-35 研磨液0.02M磷酸重金屬鉛隨研磨時間之型態變化……..81
圖4-36 研磨液0.2M磷酸重金屬鉛隨研磨時間之型態變化……...82

表目錄
表2-1 焚化系統中重金屬化合物之型態與分佈……………………....8
表3-1 實驗藥品………………………………………………………..21
表3-2 實驗材料器具…………………………………………………..21
表3-3 實驗配置表………..……………………………………………39
表4-1 反應灰物理性質………………………………………………..40
表4-2 鍋爐灰物理性質………………………………………………..40
表4-3 鍋爐灰主要組成元素分析……………………………………..44
表4-4 鍋爐灰之重金屬含量…………………………………………..44
表4-5 鍋爐灰主要組成元素分析……………………………………..45
表4-6 反應灰之重金屬含量…………………………………………..45
表4-7 反應灰毒性溶出程序…………………………………………..48
表4-8 飛灰毒性特性溶出程序………………………………………..48
表4-9 水洗灰之元素分析……………………………………………..54
表4-10 水洗灰之重金屬含量…………………………………………54
表4-11 水洗灰毒性特性溶出程序……………………………………56
表4-12 研磨水洗灰TCLP溶出濃度….…..…………………………69
表4-13 添加PbO研磨後鉛TCLP溶出濃度……….………………73
表4-14 使用磷酸研磨液鉛TCLP溶出濃度…………………………77

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