臺灣博碩士論文加值系統

本研究主要以管柱實驗作為推求實場設置之操作參數，以及建置後可能產生的問題。零價鐵將硝酸鹽氮還原成氨氮，但由於鐵粉表面保護膜(表面氧化物)的影響，因此未經前處理鐵粉去除率只有30 %。保護膜可以利用還原劑或酸洗去除，實驗結果降解效率提升到80 %以上，其中酸洗前處理對於去除保護膜的成效較佳。鐵粉使用壽命評估方面，1克45μm零價鐵經過酸洗後可降解1.7 ~ 2.1毫克的硝酸鹽氮，鐵粉的使用率只有3.42 %。在鐵粉再利用驗證鐵粉只有表面反應，管柱反應過程鐵粉由灰白色轉變為深黑色，由化學分析電子光譜儀（ESCA）分析顯示零價鐵轉化為Fe2O3。出流水中pH值的變化與起始硝酸鹽濃度、起始pH值與去除率的好壞有關；在ORP方面均有下降的趨勢。在實場設置時建議使用pH值作為操作參數。通量大小與去除率成反比，鐵粉填充量與管柱操作時間成正比。
實場設置問題在於管柱阻塞產生，造成阻塞的原因為無機物因pH上升造成沉澱，包含Fe2O3、FeCO3、CaCO3。鐵砂混合可以解決阻塞問題，但會減少管柱的操作時間。在模場放大部分，實驗結果顯示去除率維持在85 %以上。
反應區間(transfer zone)的大小與轉速、通量成正比。利用還原劑前處理的反應區間大於酸洗前處理。酸洗前處理5 r.p.m/(157 cm3/cm2 day)之反應區間為1.85 ~ 3.03公分。反應速率常數方面，酸洗前處理鐵粉適用Thomas式，當R2大於0.8以上時，反應速率常數介於0.0240 ~ 0.0553 ( L/mg-day )。
模場放大的部分，使用動力學方法推估模場放大的貫穿體積與貫穿時間誤差較小。在金屬牆設置方面，文獻中金屬牆配置量介於93 ~ 4149（kg/m2），但本研究中鐵粉配置量均小於1 kg/m2，配置量較小的原因為零價鐵有經過前處理。

Laboratory scale column tests were conducted to obtain the field design parameters and possible operation problems after field installation.
For the nitrate contaminant water made in the laboratory, nitrate reduction by zero-valent iron was found affected by the coating or metal oxide on the ZVI surface. Without pretreatment of ZVI, nitrate removal rate was only 30%. Surface coating can be removed by strong reduction agent (NaBH4) or acid washing, but acid washing was shown better efficiency in this study. In the column tests, 1 mg ZVI can only remove 2.14 mg nitrate and the used ZVI was only 3.42% according to the stoichiometric ratio, and which is an evidence of surface reaction for the ZVI. The reduction of ZVI becomes iron oxides coating on the ZVI surface. In the column test, iron color was grayish in the beginning (pure ZVI) and became deep black after the ZVI was used. Effluent soluble iron concentration was below 1 mg/L. ESCA analysis was conducted for the surface species of the ZVI and Fe2O3 was found on the coated surface. Effluent pH was directly related to the initial nitrate concentration and removal rate and effluent ORP was decreased during the experiment. Therefore, pH is suggested as an indicator for nitrate removal efficiency for field operation. Increasing flux leads to increasing nitrate removal percentage. For the same flux, hydraulic resident time (HRT) and removal rate had no relationship, but higher HRT would increase operation time.
The problem for field operation (using actual groundwater) was the clogging in the column. The reason for clogging was due to mineral precipitates after the increased pH and gas production. The mineral precipitates include Fe2O3, FeCO3, CaCO3. ZVI mixed with sand in the column can solve the clogging, but operation time was decreased.
Transfer zone in the column were proportionately related to flow rate and flux. For pretreated ZVI by acid wash (5 r.pm with 157 cm3/cm2day), transfer zone were from1.85 to 3.03 cm and real hydraulic retention time were from 10 to 16 minutes. For determination of reaction constants, Thomas Equation was applicable, where R square was above 0.8 and reaction constants were between 0.0240 and 0.0553 (L/mg-day).
Column tests were scaled up using two methods including Kinetic Approach and Scale-Up Approach. The differences were small comparing the calculated to the actual breakthrough volume and time using Kinetic Approach. For calculation of PRB installation, W/A (mass of zero-valent iron/cross-sectional plume) was below 1 kg/m2, and iron well was below 16 cm. It was low comparing to the literature value and it was due to that the ZVI used in this study was pretreated.

目 錄
中文摘要 i
英文摘要 ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 ix
第一章　前言 1
1.1　研究緣起 1
1.2　研究目的 2
1.3　研究方法 2
第二章　文獻回顧 5
2.1 地下水污染特性 5
2.1.1 硝酸鹽氮之污染與危害 7
2.1.2 現行飲用水法規 9
2.1.3 我國地下水污染事件簡介 10
2.2 地下水污染之整治方法 12
2.2.1 離地處理 13
2.2.2 現地處理 14
2.2.3 淨水場對於硝酸鹽的處理程序 16
2.3 零價鐵降解硝酸鹽氮理論 18
2.4 金屬牆建置理論 20
2.4.1 金屬牆建置流程 21
2.4.2 現行金屬牆實場介紹 28
2.5 零價鐵管柱理論 31
2.5.1 國外研究 31
2.5.2 國內研究 34
第三章　研究內容與實驗方法 37
3.1 研究內容 37
3.2 實驗方法 38
3.2.1 實驗設計 45
3.2.2 實驗器材與藥品 47
3.2.3 實驗配置 50
3.2.4 分析方法 51
第四章　結果與討論 52
4.1 未經前處理鐵粉對硝酸鹽降解效果 52
4.1.1 鐵粉填充量與流量 52
4.1.2 控制實驗中溶氧值 58
4.2 前處理鐵粉對硝酸鹽降解效果 63
4.2.1 還原劑前處理 63
4.2.2 酸洗前處理 73
4.3 模場各項參數探討 82
4.3.1 pH值變化 82
4.3.2 ORP變化 83
4.3.3 氨氮變化 84
4.3.4 鐵離子變化 85
4.3.5 水力停留時間(HRT) 87
4.3.6 通量變化 89
4.4 零價鐵粉使用壽命評估 90
4.5 反應速率常數與半衰期計算 93
4.5.1 反應區間計算方法 93
4.5.2 Thomas式計算方法 98
4.6 實場地下水模擬情形 101
4.7 模場放大 105
4.7.1 模場放大實驗結果 105
4.7.2 模場放大推估 107
4.8 零價鐵表面分析 110
4.9 金屬牆配置的應用 114
第五章　結論與建議 117
5.1 結論 117
5.2 建議 118
參考文獻 120
附錄
A 符號彙編 125

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