臺灣博碩士論文加值系統

近年來由於工商業發展迅速，每年約產生600萬噸的廢棄物，傳統掩埋方式已無法有效處理日益增加之廢棄物，故政府於97年2月完成24座大型焚化爐之興建，期能有效解決廢棄物所衍生的相關問題。據環保署97年統計資料顯示，目前國內近90%清運垃圾雖以都市固體廢棄物焚化爐(Municipal Solid Waste Incinerators, MSWI)處理，卻會伴隨底渣及飛灰產生，產生量為0.044 (ton Fly ash/ ton Solid waste)。由國內24座大型焚化爐之MSWI飛灰TCLP檢測結果顯示，焚化飛灰中重金屬鉛(Pb)含量平均濃度約為50 mg/L，為法規標準值5.0 mg/L十倍以上，且TCLP不合格率高達52.9%。若飛灰未經適當之穩定/安定化處理，將可能造成重金屬環境汙染。
飛灰具有高pH之特性，故重金屬多以氫氧化物形式沉積於飛灰上；因此本研究以酸洗程序，將飛灰中重金屬鉛(Pb)及銅(Cu)溶出，再利用電沉積技術進行酸洗液後續處理。目的在於探討，酸洗程序對飛灰重金屬溶出能力及電沉積技術於酸洗液中回收重金屬之效能。
研究結果顯示，以液固比20/1之0.5N HNO3酸洗飛灰，酸洗後重量削減68.6%；鉛及銅溶出率分別為55.6%及83.2%；重金屬鉛的鍵結型態殘渣態比例由34%上升至66%。由電沉積實驗結果得知，供應電流5A、10A、15A之鉛去除率分別為54%、74%、84%；銅分別90%、80%、82%。以回收率而言，固定電流10A可回收25.7%鉛及59.8%銅之效果最好。結果顯示，以酸洗結合電沉積用來回收MSWI飛灰中重金屬是可行的。

In recent years, because the industry and commerce is fast growing, there''re almost 6 million tons of domestic wastes produced every year. It''s unable to dispose of the domestic wastes effectively by traditional landfill, so the government finished the construction of 24 large-scale incinerators in February 2008. According to EPA statistic in Taiwan, it''s nearly 90% of domestic wastes was treated by Municipal Solid Waste Incinerators (MSWI), but it will produce bottom-ash and fly-ash. The producing amount is 0.044 ton Fly ash/ ton Solid waste. And the MSWI fly ash TCLP (Toxicity Characteristic Leaching Procedure) test results showed that the average concentration of heavy metal lead was about 50 mg/L, which is ten times over the regulation limit 5.0 mg/L, and TCLP disqualification rate is up to 52.9%. If fly ash don’t take treatment through appropriate stability / solidification, it may cause the environmental pollution of heavy metal.
The fly ash usually has characteristic of high pH, so that much heavy metal is deposited on the fly ash in the form of hydroxide. This research will dissolve Pb and Cu from fly ash by acid washing, and then utilize electrodeposition technology to deal the acid-washing liquid. The purpose is wanted to discuss the ability of dissolving heavy metal by acid-washing procedure, and the efficiency of electrodeposition technology to recover the heavy metal from acid-washing liquid.
The results of study reveal that acid-washing the fly ash by L/S=20/1 with 0.5N HNO3 could cut down the weight by 68.6% after acid-washing. The dissolution rates of Pb and Cu are 55.6% and 83.2% respectively, and then the residue rates of Pb rises from 34% to 66%. By means of electrodeposition experiment, the removing rates of Pb at electric current 5A, 10A, 15A are 54%, 74%, 84% respectively; Cu is differentiated 90%, 80%, 82%. As for rate of recovery, it''s the best to fix electric current at 10A which can recover 25.7% of the Pb and 59.8% of Cu. The results reveal that it can be looked forward to recover heavy metal from MSWI fly ash by the combined procedure with acid-washing and electrodeposition.

誌謝 i
中文摘要 iii
ABSTRACT v
總目錄 vii
圖目錄 xi
表目錄 xiii
第一章 研究目的 1
1.1研究動機 1
1.2研究目的與內容 3
第二章 文獻回顧 5
2.1台灣焚化爐及焚化飛灰之產量 7
2.1.1焚化灰渣之來源 7
2.1.2焚化灰渣種類之分類 8
2.2都市垃圾焚化飛灰之組成與特性 9
2.2.1焚化飛灰之物理和化學特性 9
2.2.2焚化飛灰之化學組成 11
2.3都市垃圾焚化飛灰之重金屬及處理方式 14
2.3.1焚化飛灰重金屬來源 14
2.3.2焚化飛灰重金屬溶出特性 15
2.3.3都市垃圾焚化飛灰常見處理方式 17
2.3.4飛灰中重金屬處理後資源化與再利用之應用潛勢 20
2.4金屬型態之分佈及其影響因子 22
2.4.1金屬在飛灰中的鍵結型態 22
2.4.2重金屬在飛灰中鍵結型態的影響因子 24
2.4.3重金屬於污染物中鍵結型態之相關研究 24
2.5酸洗相關研究 26
2.6電沉積之技術 29
2.6.1電化學應用與原理 29
2.6.2電沉積法之作用機制 29
2.6.3影響電沉積鍍層之參數 30
2.6.4循環伏安電沈積法 31
2.6.5電沉積法之相關研究 32
2.7文獻總結及研究方向 35
第三章 材料與方法 39
3.1實驗設備與材料 40
3.1.1 MSWI 飛灰採樣及前處理 40
3.1.2電沉積實驗裝置 40
3.1.3實驗藥品材料 41
3.1.4實驗設備及儀器 44
3.2實驗流程 45
3.3飛灰基本性質分析 46
3.3.1廢棄物之氫離子濃度指數（pH值）測定方法 46
3.3.2水中導電度測定方法－導電度計法 47
3.3.3水中氯鹽檢測方法－硝酸汞滴定法 47
3.3.4廢棄物含水份測定方法－間接測定法 48
3.3.5土壤中陽離子交換容量－醋酸鈉法 48
3.3.6毒性特性溶出試驗( TCLP ) 49
3.3.7土壤中重金屬檢測方法－王水消化法 51
3.3.8逐步萃取分析 52
3.3.9殘渣態 55
3.4酸洗飛灰實驗 56
3.4.1酸洗溶液之選擇 56
3.4.2酸洗飛灰實驗 56
3.5電沉積實驗 58
3.5.1電沉積實驗方法 58
3.5.2電沉積質量平衡 58
第四章 結果與討論 61
4.1飛灰基本特性分析結果 61
4.2飛灰重金屬濃度分析 63
4.2.1總量分析 63
4.2.2鍵結型態分析 63
4.2.2.1鉛(Lead)鍵結型態分佈 63
4.2.2.2銅(Copper)鍵結型態分佈 65
4.2.2.3 重金屬總量與逐步萃取分析之比較 67
4.3飛灰之有害特性認定 69
4.4酸洗飛灰實驗 70
4.4.1酸洗溶液選擇 70
4.4.2飛灰減量化研究 71
4.4.3酸洗飛灰實驗 72
4.5電沉積實驗 74
4.5.1電沉積實驗觀察項目 74
4.5.2經電沉積作用酸洗液重金屬濃度變化 77
4.5.2.1鉛(Lead)濃度及去除率變化情形 77
4.5.2.2銅(Copper)濃度及去除率變化情形 78
4.5.3無迴流/迴流電沉積之酸洗液重金屬濃度變化 80
4.5.4氯鹽濃度變化 81
4.5.5電沉積後沉澱物/懸浮固體分析 82
4.5.6電沉積後沉積物分析 83
4.5.7質量平衡分析 86
4.6經濟效益評估 88
4.6.1酸洗經濟效益評估 88
4.6.2電沉積經濟效益評估 88
4.7與其他處理技術做比較 90
第五章 結論及建議 95
5.1結論 95
5.1.1酸洗飛灰實驗 95
5.1.2電沉積實驗 96
5.2建議 97
參考文獻 99
附錄 107
一、原子吸收光譜儀檢量線 107
二、電沈積實驗原始數據 109

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