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研究生: 陳仕洲
Chen, Shiu-chou
論文名稱: 移動性污染源排放廢氣中戴奧辛/呋喃之特徵
PCDD/F Characteristic in the Exhaust of Mobile Sources
指導教授: 李文智
Lee, Wen-jhih
學位類別: 碩士
Master
系所名稱: 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年: 2008
畢業學年度: 96
語文別: 中文
論文頁數: 276
中文關鍵詞: 移動性污染源排放係數氣固相分佈車輛戴奥辛
外文關鍵詞: vehicle, gas- and particulate-phase distribution, PCDD/Fs, mobile source, emission factor
相關次數: 點閱:106下載:20
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  • 移動性污染源排放PCDD/Fs對於國內PCDD/Fs之貢獻量影響日益顯著,為瞭解移動性污染源排放PCDD/Fs之特徵,本研究針對50輛汽油SUV車、15輛柴油小客車、2輛重型柴油車及10輛機械腳踏車,進行PCDD/Fs排放之研究,藉由行車型態測試進行排氣PCDD/Fs檢測分析,以建立國內移動性污染源PCDD/Fs之排放廢氣特徵剖面,另外,將其排放廢氣之PCDD/Fs進行氣相及固相分析,並將結果與國內外相關研究文獻比較,提供國內後續進行管制移動性污染源排放PCDD/Fs之參考。
    本研究車輛排放廢氣中PCDD/Fs之濃度,其範圍介於0.00943~0.234 ng I-TEQ/Nm3之間,其中SUV車、柴小客車、重型柴油車及機械腳踏車排放廢氣中之PCDD/Fs平均濃度分別為0.0553、0.0417、0.145及0.0591 ng I-TEQ/Nm3;車輛PCDD/Fs排放係數其範圍介於0.0267~2.91 ng I-TEQ/km之間,SUV車、柴小客車、重型柴油車及機械腳踏車之排放係數分別為0.113、0.105、1.86及0.0831 ng I-TEQ/km。
    4種車款PCDD/Fs固相之I-TEQ毒性百分比分別為:SUV車之74.4%;柴油小客車之91.8%;重型柴油車之70.2%;機械腳踏車之85.1%, 4種車款固相I-TEQ毒性百分比平均為79.8%,即各車款排放廢氣之PCDD/Fs均以固相較具優勢,因此降低車輛粒狀物之排放,可有效管制車輛排放戴奧辛。
    本研究為瞭解新舊機油對於移動性污染源排放PCDD/Fs之影響,選取L與N 兩車款機械腳踏車分別使用舊機油與新機油進行排放測試,發現固相PCDD/Fs總I-TEQ濃度,分別減少38.2%(0.0445降低至0.0275 ng I-TEQ/Nm3) 及58.2%(從0.0631降低至0.0264 ng I-TEQ/Nm3) ,總I-TEQ排放係數亦分別減少53.5%(0.141降低至0.0655 ng I-TEQ/km)及56.6%(0.105 降低至0.0456 ng I-TEQ/km),其固相PCDD/Fs之I-TEQ濃度及排放係數均有明顯下降之趨勢,故更換新機油,應有助於減少固相PCDD/Fs之生成。
    為瞭解移動性污染源排放對周界大氣之影響,進行焚化廠周界大氣採樣,結果顯示M廠大氣PCDD/Fs總I-TEQ平均濃度為0.0418 pg I-TEQ/Nm3,將M廠之各採樣點周界大氣PCDD/Fs特徵剖面與其煙道廢氣PCDD/Fs特徵剖面及分汽油休旅車、柴油小客車、重型柴油車之特徵剖面進行主要成分分析,結果顯示M廠周界大氣與其煙道廢氣之PCDD/Fs之特徵剖面並無明顯關聯性,而與汽油休旅車、柴油小客車、重型柴油車排放廢氣之PCDD/Fs特徵剖面相近,推測其周界大氣PCDD/Fs之濃度應受到周界移動污染源影響。

    For these years, mobile pollution emission sources have contributed more and more in domestic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), This study examined the characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the exhaust gases of mobile sources. In this study, 50 vehicles of petrol SUV car, 15 vehicles of diesel oil limousine, 2 heavy-duty diesel vehicles and 10 motorcycles were investigated.
    The PCDD/Fs emission factors of mobile sources were determined‚ and the overall emission quantity of PCDD/Fs from the domestic mobile sources was estimated. Finally, the influence of these emission sources on the surrounding environment was assessed.
    The total PCDD/F concentrations exhaust from SUV, diesel vehicles, heavy-duty diesel vehicles and motorcycles are 0.0553, 0.0417, 0.145 and 0.0591 ng I-TEQ/Nm3, respectively. The PCDD/F emission factors from SUV, diesel vehicles, heavy-duty diesel vehicles and motorcycles are 0.113, 0.105, 1.86 and 0.0831 ng I-TEQ/km, respectively.
    The particulate-phase of PCDD/Fs in the exhaust gases of SUV, diesel vehicles, heavy-duty diesel vehicles and motorcycles are 74.4%, 91.8%, 70.2% and 85.1%, respectively. Moreover, the mean I-TEQ concentration in particulate-phase is 79.8%. Due to the relatively high fraction of PCDD/Fs in particulate-phase, the PCDD/Fs emission can be effectively controlled by reducing the emission of particle in the exhaust gases of vehicles.
    After using new engine oil old engine oil, the PCDD/Fs concentrations in particulate-phase were reduced 38.2% (from 0.0445 to 0.0275 ng I-TEQ/Nm3) and 58.2%(from 0.0631 to 0.0264 ng I-TEQ/Nm3), respectively, for L type and N type mechanical bicycles.
    The emission factors of PCDD/F I-TEQ were also reduced 53.5% (from 0.141 to 0.0655 ng I-TEQ/km) and 56.6% (from 0.105 to 0.0456 ng I-TEQ/km), respectively, for L type and N type mechanical bicycles.
    The trend of PCDD/F concentrations and I-TEQ emission factors indicated that using the new engine oil can reduce the PCDD/Fs emission of vehicles.
    The research result shows the average PCDD/Fs concentrations in ambient air nearby M site (municipal solid waste incinerators [MSWIs]) is 0.0418 pg I-TEQ/Nm3, we compared cross-section of above PCDD/Fs with that inside the incinerator tunnels and SUV, diesel vehicles, heavy-duty diesel vehicles and motorcycles and found that there is no prominent relationship between cross-section characteristics of PCDD/Fs around the incinerators and inside their tunnels but cross-section characteristics of PCDD/Fs around the incinerators are so similar to out test vehicles. Therefore, we predict concentration of PCDD/Fs n ambient air nearby incinerators should be affected by mobile pollution emission sources which nearby them.

    總目錄 摘要 I ABSTRACT III 致謝 V 總目錄 VI 表目錄 X 圖目錄 XIV 第一章、前言 1 第二章、文獻回顧 2 2-1 PCDD/Fs之物理化學性質 2 2-2 PCDD/Fs對人體健康及環境的可能影響 4 2-3 PCDD/Fs之形成機制 7 2-3-1 de Novo合成反應 7 2-3-2 經由前驅物質之異相觸媒合成 11 2-3-3 PCDDs與PCDFs形成機制之相異處 11 2-4國內固定污染源煙道廢氣排放戴奧辛之管制標準 14 2-5 國內、外汽、柴油車產生戴奧辛之排放清冊、排放因子相關 資料及各國管制措施及國際管制趨勢。 15 2-5-1戴奧辛之排放清冊 15 2-5-2 車輛粒狀物之排放係數 21 2-5-3汽、柴油車產生戴奧辛之排放係數 21 2-5-3-1 車輛尾氣排放之PCDD/Fs 22 2-5-3-2 隧道排放之研究 34 2-5-3-3 實車排放之研究 37 2-5-4車輛排放PCDD/Fs之相關因子 39 2-5-4-1 測試引擎之狀態 39 2-5-4-2 氯的影響 39 2-5-4-3 重金屬的影響 40 2-5-4-4 前驅物的影響 41 2-5-4-5氧的影響 41 2-5-4-6硫的影響 41 2-5-4-7機油的影響 42 2-5-5各國管制措施及國際管制趨勢 43 2-5-5-1 總芳香烴含量 46 2-5-5-2多環芳香烴含量 47 第三章、實驗設備及方法 48 3-1研究架構 48 3-2受測車輛之規劃 49 3-2-1受測車輛之選擇 49 3-2-2各車型之受測期程 51 3-3周界大氣採樣之規劃 57 3-3-1採樣點之選擇 57 3-3-2採樣期程 57 3-4 油品成分及前驅物檢測分析 60 3-4-1油品之採樣規劃 60 3-4-2 油品中之氯含量分析 67 3-4-2-1方法概要 67 3-4-2-2設備及材料 67 3-4-2-3 試劑 68 3-4-2-4 步驟 68 3-4-2-5 結果處理 69 3-4-2-6品質管制 70 3-4-3油品中之多環芳香烴分析 71 3-4-3-1方法概要 71 3-4-3-2 設備及材料 72 3-4-3-3 試劑 73 3-4-3-4 步驟 73 3-4-3-5 結果處理 75 3-4-3-6 品質管制 76 3-5車輛廢氣採樣及分析方法 80 3-5-1 污染行車型態檢測 80 3-5-1-1 FTP-75行車型態 80 3-5-1-2歐盟NEDC測試程序 81 3-5-1-3 US Transient Cycle測試程序 82 3-5-1-4 機車行車型態測試程序 84 3-5-2 排放管道中戴奧辛及呋喃採樣 87 3-5-2-1煙道PCDD/Fs之採樣 87 3-5-2-2煙道廢氣中PCDD/Fs樣品之前處理 103 3-6 大氣採樣分析方法 107 3-6-1大氣PCDD/Fs採樣 107 3-6-1-1 PS-1高量空氣採樣器 107 3-6-1-2 氣固相採樣模組 107 3-6-1-3 流量校正 111 3-6-1-4 PCDD/Fs大氣採樣方法 116 3-6-1-5 PCDD/Fs大氣採樣之標準流量與體積 117 3-6-2 PCDD/Fs樣品之前處理 119 3-6-2-1大氣樣品之前處理 119 3-7 儀器分析 122 3-7-1儀操作條件 122 3-7-2實驗室品管程序 127 3-7-3 車輛排放戴奧辛採樣及樣品檢測分析過程照片 128 3-8品保品管相關數據 129 第四章、結果與討論 164 4-1油品中氯及芳香烴成分 164 4-1-1油品中氯含量依不同檢測方法之比較 164 4-1-2油品中芳香烴含量 166 4-1-3測試用油品芳香烴含量 174 4-1-4油品芳香烴含量與法規值相較 174 4-2 車輛研究測試中心大氣中PCDD/Fs之濃度 176 4-3車輛排放戴奧辛之特徵 179 4-3-1 SUV車 179 4-3-2柴小客車 195 4-3-3重型柴油車 205 4-3-4機械腳踏車 209 4-4車排放廢氣中PCDD/Fs之氣固相分佈 225 4-4-1 SUV車款氣固相分佈 225 4-4-2 柴小客車款氣固相分佈 225 4-4-3 重型柴油車款氣固相分佈 232 4-4-4 機械腳踏車款氣固相分佈 232 4-5 老舊機油對車輛排放廢氣中PCDD/Fs影響 238 4-6觸媒轉化器對車輛排放廢氣中PCDD/Fs與PAHs之影響 240 4-7國內外車輛PCDD/Fs排放係數之比較 242 4-7-1 汽油汽車之排放係數 243 4-7-2 柴油車之排放係數 247 4-8機動車輛戴奧辛流佈趨勢 250 第五章 結論與建議 263 5-1結論 263 5-2建議 265 參考文獻 266 表目錄 表2-1 PCDD/FS之物化性質 3 表2-2 PCDD/FS毒性當量因子 6 表2-3 PCDD/FS生成之文獻 9 表2-4 PCDD/FS之生成速率 10 表2-5 國內固定污染源排放PCDD/FS法規管制標準 14 表2-6 汽、柴油車排放PCDD/FS與其所佔總排放量百分比 16 表2-7 美國於1987、1995及2000年主要戴奧辛排放源排序及其貢獻百分比 19 表2-8 台灣地區戴奧辛污染源之排放清單 20 表2-9車輛排放PCDD/FS之研究結果 23 表2-10柴油轎車之PCDD/FS排放係數 24 表2-11柴油卡車之PCDD/FS排放係數 25 表2-12 含鉛汽油車之PCDD/FS排放係數 26 表2-13 無鉛汽油轎車之PCDD/FS排放係數 27 表2-14 無鉛汽油轎車(有觸媒轉化器)之PCDD/FS排放係數 28 表2-15 隧道內大氣採樣推估移動污染源PCDD/FS排放係數之文獻36 表2-16 道路實車之PCDD/FS採樣 38 表2-17 不同情況下柴油車輛PCDD/FS之排放係數 38 表2-18 MK1柴油與EPEFE參考柴油之組成 44 表2-19 車用汽柴油成分及性能管制標準 45 表2-20 各國柴油規範總芳香烴含量比較表 46 表2-21 各國柴油規範多環芳香烴含量比較表 47 表3-1 SUV車選定車款相關資料 49 表3-2二期柴油汽車選定車款相關資料 50 表3-3三期柴油汽車選定車款相關資料 50 表3-4 柴油小客車選定車款相關資料 50 表3-5 機器腳踏車選定車款相關資料 51 表3-6 SUV車排放戴奧辛含量檢測期程 52 表3-7 柴小客車車排戴奧辛含量檢測期程 55 表3-8 重型柴油車排放戴奧辛含量檢測期程 56 表3-9 機器腳踏車排放戴奧辛含量檢測期程 56 表3-10 M廠與採樣點位置之二度分帶座標 59 表3-11 M廠周界介質之採樣期程 59 表3-12 現行市面油品採集規劃 61 表3-13 現行市面油品分區平均分配採集規畫 66 表3-14 NEDC行車型態諸元表 81 表3-15 PCDD/FS待測物和13C12-同位素標幟物之監測離子群 124 表3-16 PCDDS及PCDFS離子強度比之品管範圍 126 表3-17 SUV車輛排氣中PCDD/FS濃度檢測數據之MDL 130 表3-18 柴小客車輛排氣中PCDD/FS濃度檢測數據之MDL 135 表3-19 重型柴油車輛排氣中PCDD/FS濃度檢測數據之MDL 138 表3-20 機械腳踏車輛排氣中PCDD/FS濃度檢測數據之MDL 139 表3-21 SUV車標準品回收率及回收率管制範圍 140 表3-22 柴小客車標準品回收率及回收率管制範圍 145 表3-23 重型柴油車標準品回收率及回收率管制範圍 148 表3-24 四行程機械腳踏車標準品回收率及回收率管制範圍 149 表3-25 二行程機械腳踏車標準品回收率及回收率管制範圍 150 表3-26 SUV車空白添加待測物回收率及回收率管制範圍 151 表3-27 柴小客車空白添加待測物回收率及回收率管制範圍 156 表3-28 重型柴油車空白添加待測物回收率及回收率管制範圍 159 表3-29 機器腳踏車空白添加待測物回收率及回收率管制範圍 160 表3-30 M廠周界大氣樣品之標準品回收率 161 表3-31 周界大氣樣品STOCK PAR之標準品回收率 163 表4-1 以NIEA R404.21C方法及ASTM D4929方法檢測油品中氯含量165 表4-2 現行市面油品芳香烴含量 168 表4-3 現行市面油品中芳香烴含量綜合比較 173 表4-4 車輛測試研究中心測試用油品芳香烴含量 175 表4-5 現行市面油品及測試用油品芳香烴含量與法規值比較 175 表4-6 車輛研究測試中心檢驗室空氣中PCDD/FS之濃度 177 表4-7 A款車輛排放廢氣中PCDD/FS之濃度 180 表4-8 B款車輛排放廢氣中PCDD/FS之濃度 181 表4-9 C款車輛排放廢氣中PCDD/FS之濃度 182 表4-10 D款車輛排放廢氣中PCDD/FS之濃度 183 表4-11 E款車輛排放廢氣中PCDD/FS之濃度 184 表4-12 A款車輛之PCDD/FS排放係數 190 表4-13 B款車輛之PCDD/FS排放係數 191 表4-14 C款車輛之PCDD/FS排放係數 192 表4-15 D款車輛之PCDD/FS排放係數 193 表4-16 E款車輛之PCDD/FS排放係數 194 表4-17 F款車輛排放廢氣中PCDD/FS之濃度 196 表4-18 G款車輛排放廢氣中PCDD/FS之濃度 197 表4-19 H款車輛排放廢氣中PCDD/FS之濃度 198 表4-20 F款車輛之PCDD/FS排放係數 202 表4-21 G款車輛之PCDD/FS排放係數 203 表4-22 H款車輛之PCDD/FS排放係數 204 表4-23 I及J款車輛排放廢氣中PCDD/FS之濃度 206 表4-24 I及J款車輛排放廢氣中PCDD/FS之排放係數 208 表4-25 K款車輛排放廢氣中PCDD/FS之排放濃度 210 表4-26 L款車輛排放廢氣中PCDD/FS之排放濃度 211 表4-27 M款車輛排放廢氣中PCDD/FS之排放濃度 212 表4-28 N款車輛排放廢氣中PCDD/FS之排放濃度 213 表4-29 O款車輛排放廢氣中PCDD/FS之排放濃度 214 表4-30 K款車輛排放廢氣中PCDD/FS之排放係數 216 表4-31 L款車輛排放廢氣中PCDD/FS之排放係數 217 表4-32 M款車輛排放廢氣中PCDD/FS之排放係數 218 表4-33 N款車輛排放廢氣中PCDD/FS之排放係數 219 表4-34 O款車輛排放廢氣中PCDD/FS之排放係數 220 表4-35 本研究和國內不同地區之一般環境大氣中PCDD/FS濃度比較 222 表4-36 戴奧辛環境監測結果彙整表 223 表4-37 SUV款車輛排放廢氣中PCDD/FS之氣、固相濃度百分比 228 表4-38 柴小客車輛排放廢氣中PCDD/FS之氣、固相濃度百分比 231 表4-39 重型柴油車款排放廢氣中PCDD/FS之氣、固相濃度百分比 234 表4-40 機械腳踏車輛排放廢氣中PCDD/FS之氣、固相濃度百分比 237 表4-41 新舊機油替換車輛排放廢氣中PCDD/FS之檢測結果 239 表4-42 柴油款車輛排放廢氣中PCDD/FS與PAHS檢測結果比較 241 表4-43 本研究車輛排放廢氣之PCDD/FS排放係數 242 表4-44 無鉛汽油轎車PCDD/FS排放係數表 244 表4-45 含鉛汽油轎車PCDD/FS排放係數表 246 表4-46 柴油車PCDD/FS排放係數表 248 表4-47 M廠第一季周界大氣採樣PCDD/FS之濃度 251 表4-48 M廠第二季周界大氣採樣PCDD/FS之濃度 252 表4-49 M廠周界固定污染戴奧辛毒性年排放量 261 表4-50 M廠交流道平均日車流量 262 表4-51 台北市機動車輛數統計 262 表4-52 M廠區域移動性污染源之之PCDD/FS年排放量推估 262 圖目錄 圖2-1 PCDD/FS之結構 2 圖2-2 DE NOVO 合成過程所生成之含氯有機物 11 圖2-3 PCDDS經由2,4,5-TCP分子之直接縮合與經由自由基形成之反應路徑 13 圖2-4 推測之PCDD/FS反應路徑圖 13 圖2-5 柴油車輛排放尾氣中之PCDD/FS濃度特徵剖面 29 圖2-6 含鉛汽油車排放尾氣中之PCDD/FS濃度特徵剖面 30 圖2-7 無鉛汽油車排放尾氣中之PCDD/FS濃度特徵剖面 31 圖3-1 研究架構流程圖 48 圖3-2 M廠周界採樣點分佈圖 58 圖3-3 廢棄物中硫、氯元素含量檢測裝置圖 71 圖3-4 高效能液相層析儀系統組合示意圖 77 圖3-5 系統校正標準品層析圖 77 圖3-6 校正標準品A層析圖 78 圖3-7 柴油樣品層析圖 78 圖3-8 層析圖 79 圖3-9 國內油料樣品層析圖一 79 圖3-10 國內油料樣品層析圖二 79 圖3-11 FTP-75污染測試行車型態 80 圖3-12 NEDC污染測試行車型態 81 圖3-13 美國暫態循環測試運轉型態 83 圖3-14 甲類機車市區行車型態 85 圖3-15 乙類機車市區行車型態 86 圖3-16 煙道PCDD/FS之採樣組裝 101 圖3-17 冷凝管及XAD-2吸附劑套組 101 圖3-18 PCDD/PCDF樣品回收流程 102 圖3-19 煙道氣PCDD/FS樣品之前處理流程 106 圖3-20 PS-1高量空氣採樣器 108 圖3-21氣固相採樣模組 109 圖3-22玻璃套筒及攜帶罐 110 圖3-23以羅德斯表校正小孔流量計 112 圖3-24 PS-1採樣器現場校正圖 113 圖3-25 品管程序流程圖 127 圖4-1 車輛研究測試中心檢驗室空氣中PCDD/FS特徵剖面 178 圖4-2 A款車輛排放廢氣中PCDD/FS之特徵剖面 185 圖4-3 B款車輛排放廢氣中PCDD/FS之特徵剖面 186 圖4-4 C款車輛排放廢氣中PCDD/FS之特徵剖面 187 圖4-5 D款車輛排放廢氣中PCDD/FS之特徵剖面 188 圖4-6 E款車輛排放廢氣中PCDD/FS之特徵剖面 189 圖4-7 F款車輛排放廢氣中PCDD/FS之特徵剖面 199 圖4-8 G款車輛排放廢氣中PCDD/FS之特徵剖面 200 圖4-9 H款車輛排放廢氣中PCDD/FS之特徵剖面 201 圖4-10 I及J款車輛排放廢氣中PCDD/FS之特徵剖面 207 圖4-11 K、L、M、N及O款車輛排放廢氣中PCDD/FS之特徵剖面 215 圖4-12 SUV款車輛排放廢氣中氣相PCDD/FS之特徵剖面 226 圖4-13 SUV款車輛排放廢氣中固相PCDD/FS之特徵剖面 227 圖4-14 F、G及H款車輛排放廢氣中氣相PCDD/FS之特徵剖面 229 圖4-15 F、G及H款車輛排放廢氣中固相PCDD/FS之特徵剖面 230 圖4-16 J款車輛排放廢氣中氣相PCDD/FS之特徵剖面 233 圖4-17 J款車輛排放廢氣中固相PCDD/FS之特徵剖面 233 圖4-18 L及N款車輛排放廢氣中氣相PCDD/FS之特徵剖面 235 圖4-19 L及N款車輛排放廢氣中固相PCDD/FS之特徵剖面 236 圖4-20 M廠第一季周界大氣採樣PCDD/FS之特徵剖面 253 圖4-21 M廠第二季周界大氣採樣PCDD/FS之特徵剖面 254 圖4-22 M廠第一季採樣周界大氣採樣點之PCDD/FS等位濃度圖及風瑰圖 256 圖4-23 M廠第二季採樣周界大氣採樣點之PCDD/FS等位濃度圖及風瑰圖 257 圖4-24 M廠第一、二季各採樣點之周界大氣、固定污染源及移動污染源之廢氣PCDD/FS特徵剖面 258 圖4-25 M廠周界大氣及各種PCDD/FS排放源煙道廢氣之主要成分分析 259

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