臺灣博碩士論文加值系統

本研究採集台灣南部KT都市垃圾焚化爐(municipal solid waste incinerator, KTMSWI)之過熱器(super heater, SH)，節熱器(economizer, EC)，半乾式吸收塔(semi-dryer absorber, SDA)，袋式集塵器(fabric filter, FF)，飛灰儲存桶(fly ash pit, FAP)和底渣(bottom residue, BR)等六個單元的廢棄物樣品，分別測定其戴奧辛(PCDD/Fs)與金屬含量(共22種)並探討其特徵分佈。
焚化爐中六個系統所收集之灰渣，分別測定戴奧辛之17個異構物，結果分別為0.102 ng I-TEQ /g (SH)、0.788 ng I-TEQ /g (EC)、0.210 ng I-TEQg (SDA)、1.95 ng I-TEQ /g (FF)和0.0218 ng I-TEQ /g(BR)，另外針對飛灰儲存桶(FAP)亦測定其含量為2.04 ng I-TEQ /g (FAP)。由於SH系統之溫度為461℃，而燃燒爐溫度高達914℃故SH和BR所測得的PCDDs/Fs濃度較低；EC系統溫度約為340℃，且所測得之濃度較高，因為PCDDs/Fs於250℃-400℃會有再合成之反應，故濃度偏高；SDA操作溫度約為245℃相對比其他系統低且反應過程中添加碳酸鈣會削減系統中氯的含量，故所測得之PCDD/Fs濃度亦較低；PCDD/Fs會被活性碳所吸附後於FF系統中攔截並收集，故其濃度較高。推估其排放係數(μg /ton-waste；μg I-TEQ /ton-waste)分別為SH (42.3；0.846)、EC (326；6.12 )、SDA (58.1；1.10)、FF (1540；61.3)、FAP (2950；107)和BR (537；4.31)。研究顯示約有56%之PCDD/Fs會被FF系統所攔截，其餘回經煙道傳輸最終收集於飛灰儲存桶中，且PCDD/Fs濃度與氯含量具有顯著性的正相關。
重金屬分析結果顯示，樣品主要以Al、Fe、Zn、Ba、Pb和Cu為主，各單元中上述六種重金屬總含量分別為96.6%(SH)、96.8%(EC)、97.0%(SDA)、94.2%(FF)和96.7%(BR)；揮發性金屬包含Cd、Sn、Sb、Hg和Pb等，大多殘留於飛灰中；其他元素包括Al、Fe、Ti、V、Cu、Mn、Co、Ni、Cu、Sr、Mo、Ag、Ba和Cr6+等元素，多出現在底渣中。五個單元中總金屬量之分佈，分別為4.87%(SH)、4.26%(EC)、2.89%(SDA)、8.17%(FF)和79.81%(BR)等，故推測焚化過程中約有20.2%的重金屬會在飛灰中，而大部分則出現在底渣(79.8%)。EC樣品中的Pb濃度和FF樣品中的Hg濃度介於警告濃度與最大限制濃度之間，而Cd和Pb在FF樣品中的濃度均超過管制標準；SH、SDA和BR樣品中重金屬濃度較低，可作為資源再利用之材料。

This study determined the polychlorinated dibenzo-p-dioxins/ dibenzo- furans (PCDD/Fs) and 22 metals contents in ash in the super heater (SH), economizer (EC), semi-dryer absorber (SDA), fabric filter (FF), fly ash pit (FAP) and bottom residue (BR) in a municipal solid waste incinerator (KTMSWI).
Experimental results showed that average PCDD/FS contents in ash samples from the SH, EC, SDA, FF, FAP and BR were 0.102, 0.788, 0.210, 1.95, 2.04 and 0.0218 ng I-TEQ /g, respectively. PCDD/Fs content was very low in the SH and BR due to high temperatures (around 461°C in the SH and 914°C in combustion chamber). Conversely, total PCDD/Fs content was significantly high in ash samples from the EC (around 340°C), mainly because the temperature is within the favorable range of 250-400°C for PCDD/FS formation due to de nova reformation mechanisms. Although the SDA operated at 245°C, the PCDD/FS content decreased very significantly, mainly because the temperature was relatively low and because calcium carbonate was introduced into flue gases to dechlorinate and dilute chlorine-containing species. PCDD/Fs were captured by the active carbon in the FF. Furthermore, the duration that fly ash remained in the FF was longer than that for other incinerator units, and thus causing an increasing trend of PCDD/Fs level downstream (except the SDA). Total PCDD/Fs emission factors (μg /ton-waste; μg I-TEQ /ton-waste) in ash samples from different units were: SH (42.3; 0.846), EC (326; 6.12 ), SDA (58.1; 1.10), FF (1540; 61.3), FAP (2950; 107) and BR (537; 4.31). Most PCDD/Fs in ash were contributed by the FF (about 56%), and the generation of PCDD/Fs in ash was significant (about 35%) during the transfer process from different units to the FAP. A strong and positive correlation in a logarithmic form existed between PCDD/Fs and chlorine (Cl-) contents in ash.
The results showed that principal metals in the incinerator ash were Al, Fe, Zn, Ba, Pb and Cu. On average, these six metals accounted for 96.6%, 96.8%, 97.0%, 94.2% and 96.7% of the total metals in SH, EC, SDA, FF and BR ash, respectively. The emission factors of individual metals from different units were obtained. Volatile metals, such as Cd, Sn, Sb, Hg and Pb, were mostly in fly ash, while lithophilic metals, such as Al, Fe, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Sr, Mo, Ag, Ba and Cr+6 were mainly in bottom ash. Distribution ratios for total metals in SH, EC, SDA, FF and BR ash were 4.87%, 4.26%, 2.89%, 8.17% and 79.81%, respectively. That is, about 20.2% of total metals were in fly ash and most metals (about 79.8%) were in bottom ash. The Pb content in EC ash and Hg content in FF ash were between alarm contents and maximum legal limits, while Cd and Pb contents in FF ash exceeded the maximum legal limits. The existing transportation system for transferring fly ash from different units to a fly ash pit should be modified for recycling the valuable metals. Ash with less than the alarm content for metals content, such as ash from the SH, SDA and BR, can be reused. Ash with metals exceeding the alarm contents, such as ash from the EC and FF, should be collected and transferred to a different fly ash pit for further treatment, such as metal recycling.

誌 謝
中文摘要
英文摘要
目錄
表目錄
圖目錄
第一章 緒論 1-1
1-1研究緣起 1-1
1-2研究目的 1-2
第二章 文獻回顧 2-1
2-1焚化廠處理流程概述 2-1
2-2 國內垃圾焚化灰渣特性 2-2
2-3 國外垃圾焚化底渣處理與再利用現況 2-3
2.3.1台灣 2-3
2.3.2荷蘭 2-6
2.3.3法國 2-7
2.3.4德國 2-7
2.3.5瑞典 2-7
2.3.6丹麥 2-8
2.3.7日本 2-9
2.3.8美國 2-9
2-4 PCDD/FS之物理化學性質 2-10
2-5 PCDD/FS對人體健康及環境的可能影響 2-11
2-6 環境中PCDD/FS之來源 2-14
2-7焚化爐中PCDD/FS之分佈與宿命 2-18
2-8 PCDD/FS之形成機制 2-23
2-9 PCDDS與PCDFS形成機制之相異處 2-27
2-10金屬元素之物化特性 2-29
2-11 PCDD/FS與重金屬可行控制技術之收集 2-33
2.11.1可行之焚化爐戴奧辛控制機制 2-33
2.11.2電弧爐戴奧辛控制技術 2-45
2.11.3可行之重金屬控制技術 2-55
第三章 材料與方法 3-1
3-1 本研究焚化廠概述 3-1
3.1.1基本資料概述 3-1
3.1.2處理流程概述 3-1
3-2樣品來源 3-3
3-3飛灰、飛灰固化物、與氯離子之採樣 3-5
3-4PCDD/FS之分析 3-7
3.4.1 PCDD/FS樣品之前處理 3-7
3.4.2儀器分析 3-8
3-5飛灰中氯離子樣品分析 3-13
3-6灰渣樣品中重金屬分析 3-16
3-7重金屬樣品分析之品質管制 3-19
3.7.1重金屬樣品分析之品質管制 3-19
3.7.2採樣品質保證與品質控制之執行 3-20
3-8品質保證及品質控制 3-24
3.8.1實驗藥品與試劑 3-24
3.8.2 實驗室品管程序及分析水準 3-26
第四章 結果與討論 4-1
4-1灰渣中PCDD/FS之含量與特徵 4-1
4-2 灰渣中氯離子含量 4-17
4-3各單元中PCDD/FS排放係數特徵分佈 4-23
4-4灰渣中重金屬之含量與特徵 4-36
4.4.1不同單元重金屬含量 4-36
4.4.2各單元樣品中重金屬之排放係數 4-49
4.4.3不同單位之重金屬分佈特徵 4-54
第五章 結論與建議 5-1
5-1結論 5-1
5-2建議 5-4
參考文獻 5-5

表2-1 PCDD/Fs之物化性質 2-11
表2-2 PCDD/Fs毒性當量因子(Toxic Equivalency Factor,TEF) 2-14
表2-3 美國境內不同來源之PCDD/Fs年排放量推估表 2-16
表2-4 最重要之PCDD/Fs排放源與其所佔總排放量之百分比 2-17
表2-5 煙道廢氣之PCDD/Fs濃度（乾燥氣，11﹪含氧量） 2-19
表2-6固體與液體殘留物之PCDD/Fs之含量 2-19
表2-7 焚化爐之燃燒區中PCDD/Fs之平衡（11座焚化爐之平均值）2-21
表2-8 焚化爐之後燃燒區中PCDD/Fs之平衡（11座焚化爐之平均 值） 2-22
表2-9 焚化爐中PCDD/Fs之平衡（11座焚化爐之平均值） 2-22
表2-10 PCDD/Fs生成之文獻 2-25
表2-11 PCDD/Fs之生成速率 2-26
表2-12經由洗滌塔、袋式集塵器及活性碳吸附之組合來去除煙道 氣中之PCDD/Fs 2-35
表2-13以SCR分解煙道氣中PCDD/Fs之文獻 2-36
表2-14 SCR對燒結爐煙道廢氣中PCDD/Fs之去除率 2-39
表2-15含硫物質對PCDD/Fs之影響 2-41
表2-16吸附劑對PCDD/Fs之影響 2-43
表2-17噴射氨對PCDD/F之影響 2-44
表2-18焚化廢氣處理系統比較表 2-52
表2-19各種空污防制設施組合 2-53
表3-1台灣南部KT都市垃圾焚化爐採樣日期、垃圾投入量與灰渣產生量 (公噸/天) 3-3
表3-2 樣品最長保存時間(天)--TCLP方法 3-6
表3-3 廢棄物樣品檢測最少需要量與保存方式(NIEA R118.01B) 3-6
表3-4 PCDD/Fs待測物和13C12-同位素標幟物之監測離子群 3-10
表3-5 PCDD/Fs待測物和13C12-同位素標幟物之監測離子群（續）3-11
表3-6 PCDDs及PCDFs離子強度比之品管範圍 3-12
表3-7 採樣設備校正品質規定一覽表 3-21
表3-8 採樣品質管制規定一覽表 3-22
表3-9時窗標準品及流出順序(DB-5管柱)和層析管柱解析度標準品.3-26
表3-10 13C12-同位素標幟物組成及工作標準品溶液 3-27
表3-11起始檢量校正標準溶液組成一覽表 3-28
表3-12樣品中之17種PCDD/Fs分析MDL值(pg) 3-30
表4-1南部KT都市垃圾焚化爐各單元中灰渣PCDD/Fs含量(ng/g) 4-2
表4-2南部KT都市垃圾焚化爐各單元中灰渣PCDD/Fs含量(ng/g)(續) 4-3
表4-3南部KT都市垃圾焚化爐各單元中灰渣PCDD/Fs含量(μg/ton-waste)
.........................................................................................................4-4
表4-4 南部KT 都市垃圾焚化爐單元中灰渣PCDD/Fs 含量(μg/ton-waste)
(續)...................................................................................................4-5
表4-5 南部KT 都市垃圾焚化爐各單元中灰渣PCDD/Fs 含量(μg/MW)
.........................................................................................................4-6
表4-6 南部KT 都市垃圾焚化爐各單元中灰渣PCDD/Fs 含量(μg/MW)(續)
.........................................................................................................4-7
表4-7 國內外文獻中大型都市廢棄物焚化爐灰渣中總PCDD/Fs 之
含量............................................................................................ 4-13
表4-8 都市垃圾焚化爐灰渣樣品中水份平均百分率(%) .................. 4-17
表4-9 南部KT 都市垃圾焚化爐生垃圾元素分析中有機氯含量..... 4-18
表4-10 本研究之都市垃圾焚化爐灰渣樣品中氯離子含量(mg/g) .. 4-20
表4-11 南部RS 都市垃圾焚化爐94 年度灰渣樣品中氯離子含量(mg/g)........................................................................................................ 4-20
表4-12 南部RS 都市垃圾焚化爐93 年度灰渣樣品中氯離子含量(mg/g)
........................................................................................................ 4-20
表4-13 KT 都市垃圾焚化爐中不同單元排放係數(μg /ton-waste, μg I-TEQ
/ton-waste) ...................................................................................... 4-24
表4-14 KT 都市垃圾焚化爐中不同單元排放係數(μg /MW, μg I-TEQ /MW)
........................................................................................................ 4-26
表4-15 不同單元灰渣中重金屬含量(g/ton-ash)................................ 4-37
表4-16 不同單元逸散因子計算結果(g /ton-waste)........................... 4-50
表4-17 不同單元逸散因子計算結果(kg /MW) ................................. 4-52
表4-18KT 都市垃圾焚化爐各單元重金屬總量之排放係數(g/kWh)4-55
表4-19 重金屬總量於各單元之排放係數(g/tone-waste) ................... 4-56

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