博碩士論文 106326019 詳細資訊




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姓名 黃永吉(Yong Ji Huang)  查詢紙本館藏   畢業系所 環境工程研究所
論文名稱 含銅污泥熱處理之PCDD/Fs及dl-PCBs排放特性研究
(Characterization of PCDD/Fs and dl-PCBs Emitted from Thermal Processes of Treating Copper-Containing Sludge)
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摘要(中) 本研究擇取台灣北部三座含銅污泥處理廠(A、B及C廠)進行排氣中PCDD/Fs及dl-PCBs去除效率及排放特性研究,並探討操作參數及防制設備流程對煙道排氣與飛灰濃度之影響。研究結果顯示,三廠之APCDs均具良好除酸除塵效果,A、B及C三廠煙囪排氣之PCDD/Fs毒性當量濃度分別為0.06、6.57及0.49 ng I-TEQ/Nm3,B廠排放濃度不僅明顯高於其他兩廠,也超出法規規範(0.5 ng I-TEQ/Nm3),B廠旋風集塵灰、袋式集塵灰、C廠旋窯旋風集塵灰、煉銅爐旋風集塵灰、第一袋式集塵灰及第二袋式集塵灰均大於法規(1.0 ng I-TEQ/g),屬有害事業廢棄物,須妥善處理, B、C兩廠之防制設備對於dl-PCBs並無明顯去除效果,同源物分佈均以TeCB-77及PeCB-126為主要優勢物種,且均以氣相為主要分佈。去除效率方面,B廠ACI+袋式集塵器僅56.7%的去除效率,大幅低於本研究其他二場與先前文獻,且洗滌塔出現PCDD/Fs質量濃度上升趨勢,同源物分佈發現,三廠大部分以高氯數物種為優勢物種,但三廠分別在半乾式洗滌塔及洗滌塔後發現低氯數物種分佈上升趨勢,氣固相分佈則是通過洗滌塔或袋式集塵器後,氣相分佈明顯有上升趨勢,說明此一階段發生嚴重記憶效應。透過上述結果並比較三廠防制設備配置,本研究認為洗滌塔不適作為最後一道防制設備,並且二燃室需維持穩定使溫度位於再合成溫度區間機會降低,透過A廠半乾式洗滌塔之高去除效率發現,若以洗滌塔等裝置裝設於熱源後,具快速冷卻特性能有效提高去除效率,記憶效應之負影響也因後續還有其他防制設備迎刃而解。
摘要(英) Three copper-containing sludge treatment plants (A, B and C plants) in northern Taiwan were investigated for the removal efficiency and emission characteristics of PCDD/Fs and dl-PCBs. The effects of operating parameters and APCDs processes on PCDD/Fs and dl-PCBs of flue gas and fly ash were discussed.The results show that the APCDs of three plants have good HCl and PM removal efficiencies. The PCDD/Fs TEQ concentrations of the stacks in the three plants A, B and C are 0.06, 6.57 and 0.49 ng I-TEQ/Nm3, respectively. The PCDD/Fs concentration of Plant B is not only significantly higher than two other plants, but also exceeds the regulation (0.5 ng I-TEQ/Nm3). The PCDD/Fs concentration of cyclone ash, baghouse ash of the Plant B and the cyclone ash of the rotary kiln, cyclone ash of the copper smelting furnace, the first baghouse ash and the second baghouse ash of Plant C are all higher than the regulation (1.0 ng I-TEQ/g), and are classified as hazardous wastes and must be properly disposed of. The APCDs of Plant B and C have no obvious removal effect for dl-PCBs, and the homologue distributions are mainly TeCB-77 and PeCB-126, and they are mainly distributed in the gas phase. In terms of removal efficiency, the removal efficiency of PCDD/Fs achieved with ACI+ baghouse of Plant B was only 56.7%, which was significantly lower than the other two plants, and the PCDD/Fs mass concentration increased as flue gas passed through the wet scrubber. The distribution of homologue indicates that most of the three plants were dominated by highly-chlorinated species. After passing through the wet scrubber or the baghouse, the gas phase distribution reveals increasing trend. These results indicate that severe “memory effects” occur at these stages. Through the results and comparing the APCDs of the three plants, this study considers that the scrubber is not suitable as the final APCD, and the combustion chamber needs to be stably operated. It is found quenching mechanism can effectively inhibit PCDD/Fs formation, and the negative effect of the memory effect can be alleviated by the subsequent APCDs.
關鍵字(中) ★ 戴奧辛
★ 多氯聯苯
★ 含銅污泥
★ 銅冶煉
關鍵字(英)
論文目次 摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 XI
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 1
第二章 文獻回顧 3
2.1 戴奧辛類化合物 3
2.1.1 PCDD/Fs及dl-PCBs物理化學特性 3
2.1.2 PCDD/Fs及dl-PCBs之危害 6
2.1.3 PCDD/Fs及dl-PCBs之來源 10
2.2 含銅污泥處理業之PCDD/Fs生成/排放潛勢 13
2.2.1 國外含銅污泥熱處理之PCDD/Fs排放特性 13
2.2.2 國內含銅污泥處理業之分佈 15
2.3 熱處理過程中PCDD/Fs及dl-PCBs的生成機制 16
2.3.1 De Novo synthesis反應 16
2.3.2 前驅物異相催化反應 17
2.3.3 記憶效應 19
2.4 減少熱處理過程中PCDD/Fs及dl-PCBs之排放 23
2.4.1 避免燃燒含PCDD/Fs物質及其前驅物 23
2.4.2 減少爐內形成 24
2.4.3 去除或破壞已生成及爐內外再合成之PCDD/Fs 29
第三章 研究方法 34
3.1 研究流程及架構 34
3.2 採樣對象 36
3.3 樣品採樣程序 39
3.3.1 煙道氣中PCDD/Fs、dl-PCBs及氯化氫採樣程序 39
3.3.2 灰份樣品採樣程序 41
3.4 實驗設備、試劑及材料 41
3.4.1 實驗材料 41
3.4.2 實驗設備 42
3.4.3 實驗藥品及溶劑 42
3.5 戴奧辛類化合物樣品前處理與分析方法 43
3.5.1 煙道氣樣品萃取程序 43
3.5.2 底渣及飛灰樣品萃取程序 46
3.5.3 戴奧辛類化合物樣品淨化程序 46
3.5.4 HRGC/HRMS 分析 47
3.7 其他檢測方法 49
3.7.1 煙道氣之氣體組成 49
3.7.2 氯化氫 50
3.7.3 粒狀物 50
第四章 結果與討論 51
4.1 A廠PCDD/Fs濃度 51
4.1.1 A廠操作條件 51
4.1.2 A廠煙道氣中PCDD/Fs濃度 52
4.1.3 A廠煙道氣之PCDD/Fs同源物分佈 54
4.1.4 A廠灰份中PCDD/Fs 59
4.2 B廠PCDD/Fs濃度 64
4.2.1 B廠操作條件 64
4.2.2 B廠煙道氣中PCDD/Fs濃度 65
4.2.3 B廠煙道氣中PCDD/Fs同源物分佈 67
4.2.4 B廠灰份中PCDD/Fs濃度 72
4.3 C廠PCDD/Fs濃度 78
4.3.1 C廠操作條件 78
4.3.2 C廠煙道氣中PCDD/Fs濃度 79
4.3.3 C廠煙道氣中PCDD/Fs同源物分佈 81
4.3.4 C廠灰份中PCDD/Fs濃度 89
4.4 B、C廠之dl-PCBs 95
4.4.1 B廠煙道氣中dl-PCBs濃度及同源物分佈 95
4.4.2 B廠灰份中dl-PCBs濃度及同源物分佈 99
4.4.3 C廠煙道氣中dl-PCBs濃度與同源物分佈 103
4.4.4 C廠灰份中dl-PCBs濃度及同源物分佈 106
4.5 A、B及C廠之PCDD/Fs及dl-PCBs機制探討 110
4.5.1 三廠煙道氣中PCDD/Fs及dl-PCBs同源物分佈比較 110
4.5.2 三廠飛灰及底渣中PCDD/Fs同源物分佈比較 114
4.5.3 三廠APCDs對於PCDD/Fs之去除效率比較 117
4.5.4 三廠APCDs中PCDD/Fs之破壞、再生成及記憶效應 122
4.5.5 含銅污泥處理業之PCDD/Fs排放係數 127
4.5.6 含銅污泥處理業之PCDD/Fs最佳可行控制技術 128
第五章 結論與建議 131
5.1 結論 131
5.2 建議 133
參考文獻 134
附錄一 三廠煙道氣樣品之PCDD/Fs及dl-PCBs回收率 147
附錄二 三廠灰份樣品之PCDD/Fs及dl-PCBs回收率 149
附錄三 三廠HCl分光光度計之檢量線 151
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IARC MONOGRAPHS – 107, POLYCHLORINATED BIPHENYLS.
張書豪,洪保鎮,張木彬”含銅污泥資源化過程中戴奧辛物種分佈特性檢測研究期末報告”,中央大學環境工程研究所,2008。
黃永吉,徐晏貞,練建國,阮維達,鄭明敏,張木彬”含銅污泥處理程序之戴奧辛生成特性與控制效率研究期末報告”,中央大學環境工程研究所,2019。
公私場所固定污染源申報空氣污染防制費之粒狀污染物、鉛、鎘、汞、砷、六價鉻、戴奧辛排放係數、控制效率及其他計量規定,行政院環保署,2018。
指導教授 張木彬(Moo Been Chang) 審核日期 2019-8-16
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