吳先琪Wu, Shian-chee臺灣大學:環境工程學研究所謝彩虹Che, Choi-hongChoi-hongChe2010-05-102018-06-282010-05-102018-06-282008U0001-2507200816401600http://ntur.lib.ntu.edu.tw//handle/246246/181565以直接注入零價鐵之方式來處理受含氯有機物污染之地下水，已有廣泛之研究及應用。然因鐵顆粒於地下環境中之低傳輸性而侷限了此法之成效及提高處理之成本，因此若能以表面改質之方法提高奈米鐵顆粒於多孔性介質中的傳輸性，必能彰顯此整治方法之優勢。研究加入不同之穩定分散劑以批次式製備奈米級懸浮液，並探討其穩定分散之能力。其中以聚丙烯酸 (PAA) 為分散劑以及最終PAA及總鐵之濃度均為5000ppm時有最好之懸浮性。所得之奈米鐵懸浮液可於28天後仍持續90%以上之懸浮效果。鐵顆粒之平均粒徑約為87 nm。SEM-EDS 觀察顯示奈米鐵顆粒似包裹於含氧量較高之穩定分散劑中 ，基本之粒徑約為200 nm左右。以奈米鐵懸浮液注入10 cm、20 cm及30 cm之土柱實驗中，其濃度之穿透率分別為75.6 %、61 %及41 %，經計算得知奈米鐵顆粒隨距離被滯留之衰減係數κ為0.01cm-1。後以顆粒之表面性質分析及土柱穿透試驗之結果撰寫奈米鐵顆粒於土壤中傳輸之模式。模式之內容為以楔型管模擬土壤顆粒之孔洞，在楔型管內對粒子進行跡軌分析以探討其於土壤表面之吸附情況，使得顆粒穿透土柱之情況在電腦之計算中重現。比較鐵顆粒穿透10cm土壤時穿透率之模擬值與實驗值可發現，模式有高估之現象。假設此誤差為被過濾粒子之粒徑於楔型管內改變而導致，調整粒徑為1000 nm 、堵塞係數α為5及考慮布朗運動造成之影響時，模擬之結果與實驗結果則較為吻合。Direct injection zero valent iron method has been widely used for treating chlorinated hydrocarbon contaminated groundwater aquifers. However, the efficiency decreases and the cost rises due to the poor spreading ability of iron particles in the subsurface environment. Therefore, if we can enhance the spreading ability of iron in porous media by adding surface modifier we may increase the applicability of iron particles.e used different stabilizing to produce nanoscale iron suspension by means of batch experiments. Also we evaluated the performance of the stabilizing dispersants. It was found that PAA can get the most stable suspension when the final concentration of PAA and total iron were both 5000 ppm. About 90% of the nano-particles remained in suspension for 28 days. The average particle sizes was 87 nm determined by ZetaSizer. Particle sizes were all found to be around 200 nm and the particles seemed to be wrapped in high oxide-containing stabilizing dispersants under the examination with SEM-EDS. ercolation rates of nanoscale iron particles through the soil was tested using column experiments. The percolation results for soil columns with depth of 10 cm, 20 cm and 30 cm were 75.6%, 61%, and 41%, respectively; and the decay coefficient (κ) of the suspended nanoscale iron particles per unit distance was 0.01 cm-1 transport model of NZVI in saturated soil layer was constructed. The pore structure in soil layer was characterized by the constructed tube model. The absorbing situation of particle of soil surface was determined by trajectory analysis in the constricted tube. The modeling analyses and experimental results indicate that the prediction has over estimated the breakthrough concentration . Simulation value relatively conforms the experimental value when adjusting the diameter of the particles and considering Brownian forces.中文摘要文摘要錄……………………………………………………………………..…..I目錄…………………………………………………….……………….V目錄…. ……………………………………………………………...….X號說明 ..................................................................................................... XI一章 前言 ............................................................................................... 1.1 研究緣起 ...................................................................................... 1.2 研究目的與內容 .......................................................................... 3二章 文獻回顧 ....................................................................................... 5.1 地下含水層之污染 ...................................................................... 5.1.1 含氯有機物之污染現況 ..................................................... 5.1.2 受含氯有機物污染之地下含水層之整治復技術 ............ 9.1.3 以奈米級零價鐵顆粒處理受污染之地下水 ..................... 9.2 奈米顆粒之穩定性探討 ............................................................ 12.3 奈米顆粒間之作用力 ................................................................ 13.3.1 DLVO 理論 ........................................................................ 15.3.2 立體效應之理論 ............................................................... 18.4 穩定分散劑 ................................................................................ 20.5 奈米顆粒在地下水層中之傳輸行為 ........................................ 22.6 膠體粒子於多孔性介質傳輸現象之模擬 ................................ 24.6.1 軌跡吸附理論 ................................................................. 26I.6.2 楔型管模型內的流場分佈 ............................................... 27.6.3 粒子間之力平衡 (Langevin 方程式) ............................. 31.6.4 顆粒之外力 ( DLVO 理論) ............................................. 34.6.5 減速效應 (retardation effect) ........................................... 35.7 奈米顆粒在地下水層中之傳輸行為的模擬方法.................... 35三章 研究方法 ..................................................................................... 37.1 研究架構 .................................................................................... 37.2 穩定分散奈米鐵懸浮液之製備 ................................................ 39.2.1 以批次式製備奈米鐵懸浮液 ........................................... 39.2.2 以迴流式流製備奈米鐵懸浮液 ....................................... 42.3 奈米鐵顆粒貫穿土壤管柱試驗 .................................................. 43.3.1 土壤樣品來源及前處理 ................................................... 43.3.2 土壤樣品一般性質分析 ................................................... 43.3.3 土柱管柱之塡充 ............................................................... 45.3.4 奈米零價鐵溶液貫穿土柱試驗 ....................................... 48.3.5 貫穿土柱試驗後奈米鐵懸浮液中鐵物種之分析 .......... 48.4 奈米鐵顆粒之特性分析 ............................................................ 49.4.1 火焰式原子吸收光譜儀 (AA) ......................................... 49.4.2 掃瞄式電子顯微鏡 (SEM) .............................................. 50.4.3 雷射奈米粒徑暨界面電位量測儀 (ZetaSizer)............... 50.5 奈米顆粒在土壤中傳輸之模式 ................................................ 52.5.1 模式建立 ........................................................................... 52.5.2 收集器之粒徑分佈 ........................................................... 57II.5.3 粒子在收集器內之軌跡分析 (trajectory analysis) ......... 57.5.4 粒子之吸附判定與收集器之堵塞判定 ........................... 62.5.5 粒子行進路線之選擇 ....................................................... 63.5.6 收集器之管徑變化 ........................................................... 63.6.7 粒子通過收集器後之穿透率 ........................................... 64四章 結果與討論 ................................................................................. 67.1 奈米鐵懸浮液之懸浮結果 ........................................................ 67.1.1 以批次式製備奈米鐵懸浮液之懸浮結果 ....................... 67.1.2 以迴流式製備奈米鐵懸浮液之懸浮結果 ....................... 76.2 奈米鐵懸浮液之特性分析 ........................................................ 78.2.1 奈米鐵顆粒之粒徑分佈 ................................................... 78.2.2 奈米鐵懸浮液之性質 ....................................................... 81.2.2 奈米鐵懸浮液之穩定性 ................................................... 88.2.4 以掃描式電子顯微鏡 (SEM) 觀察奈米鐵顆粒 ............ 90.3 土壤一般性質分析結果 ............................................................ 92.4 奈米鐵懸浮液之土壤管柱實驗 ................................................ 94.4.1 奈米鐵懸浮液穿透10 cm 土壤之初步試驗 (先以PAA 潤) ................................................................................................ 94.4.2 奈米鐵懸浮液穿透20 cm 土壤之初步試驗 (先以PAA 潤) ................................................................................................ 97.4.3 以500 mL 之奈米鐵懸浮液貫穿10 cm 土壤之初步試驗先以PAA 潤洗)......................................................................... 98.4.4 奈米鐵懸浮液穿透10 cm 土壤之試驗 (先低氧水潤洗)V.................................................................................................. 101.4.5 奈米鐵懸浮液穿透20 cm 土壤之試驗 (先低氧水潤洗).................................................................................................. 102.4.6 奈米鐵懸浮液穿透30 cm 土壤之試驗 (先低氧水潤洗).................................................................................................. 103.5 奈米鐵懸浮液穿透土柱之模擬結果 ...................................... 105.5.1 奈米鐵與土壤表面之關係 ............................................. 105.5.2 系統尺度對粒子穿透率之影響 ..................................... 107.5.3 模擬結果與實驗結果比較 ............................................. 109.5.4 以較大之平均粒徑模擬土柱實驗 ................................. 110.5.5 收器集孔徑對粒子穿透率之影響 ................................. 114.5.6 平均流速對粒子穿透率之影響 ..................................... 115五章 結論與建議 ............................................................................... 117.1 結論 .......................................................................................... 117.2 建議 .......................................................................................... 119amp;#63851;考文獻 ................................................................................................... 121錄A 實驗數據 .................................................................................. 附-1錄B 模擬結果 ................................................................................ 附-16錄C 模擬模式 ................................................................................ 附-26application/pdf2347540 bytesapplication/pdfen-US奈米鐵懸浮液聚丙烯酸傳輸模擬DLVO理論多孔性介質軌跡分析nanoscale iron particle suspensionPAAtransport modelDLVO theoryporous mediatrajectory analysisthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/181565/1/ntu-97-R95541121-1.pdf