李公哲臺灣大學：環境工程學研究所王耀晟Wang, Yao-ChengYao-ChengWang2007-11-292018-06-282007-11-292018-06-282005http://ntur.lib.ntu.edu.tw//handle/246246/62664摘要 本研究將腐植質以DAX-8樹脂分離成親水性與疏水性水樣，進行UF薄膜外加電場掃流過濾程序，並且於3種不同膜孔大小之薄膜及施加4種電場強度下進行實驗操作，於未施加電場的情況下，親水性水樣的通量衰減大於疏水性水樣，薄膜膜孔大者通量衰退程度大於膜孔小者，腐植質去除率方面是膜孔小者去除率高，親水性水樣則因較易積垢反而使去除率高於疏水性水樣，以阻力串聯分析積垢情形，發現親水性水樣主要造成不可逆積垢，而疏水性水樣則是可逆與不可逆積垢較為平均，故在清洗操作上，疏水性水樣與親水性水樣相較，更具工程應用優勢。 於施加電場的情況下過濾腐植質，過濾通量隨電場強度增加而增高，薄膜積垢阻力藉由施加電場所引起電泳動作用有效減少，分析積垢形式發現電場作用使親疏水性水樣之總積垢阻力均可減少，去除率方面隨電場增高而提升，顯見電泳作用使膜面腐植質濃度降低，因此能提高薄膜對NOM的去除，但即使於高電場強度作用下，去除率仍與薄膜膜孔大小高度相關，顯示於外加電場程序下，膜孔大小仍是影響去除率高低的重要因素，但施加電場能輔助提高去除率；不同親疏水性水樣於外加電場程序的表現不論是減緩積垢進而增加過濾通量或是提升去除效率的表現，都是疏水性水樣比較優異，與粒子電泳動試驗比較，發現疏水性水樣粒子電泳動能力較高，推論粒子電泳動能力與薄膜外加電場程序之成效具正相關性，結論是此薄膜外加電場程序適合處理電泳動能力較高的疏水性水樣，可以明顯提高過濾通量及去除效率，且就總淨出水量加以評估，疏水性水樣則較親水性之水樣可有效增加，故對原水中之腐植質成分含疏水性NOM比例較多之情況下，更顯外加電場之UF薄膜過濾應用潛力。 關鍵字：天然有機物、親疏水性、外加電場薄膜程序、膜孔大小Abstract In this study, NOM fractionation by DAX-8 resin has been used to obtain hydrophobic and hydrophilic NOM solution. The effect of hydrophobicity on electric enhanced membrane process under three pore sizes of membrane and different electric field strength were investigated. When electric field was not applied, hydrophilic NOM solution caused more flux decline than hydrophobic one. The flux decline was getting worse with increasing pore size, while the NOM rejection was getting better with decreasing pore size. Besides, hydrophilic NOM solution resulted in significant NOM rejection due to the greater fouling as compared to the hydrophobic sample. Through the calculation of series resistance for membrane, it was observed that the hydrophilic components largely contributed to irreversible resistance but the reversible/irreversible resistance caused by the hydrophobic components was quite similar. Membrane cleaning operations such as backwash, chemical cleaning were more economical for hydrophobic NOM solution. Accordingly, hydrophobic NOM solution is more applicable to water treatment than hydrophilic one. When an electric field was applied, flux increased with the strength of the electric field. Direct current electric field could be used to reduce the fouling resistance by the electrophoresis effect. By analyzing the fouling resistances, the total fouling resistances of hydrophobic and hydrophilic NOM solutions were both reduced with the electric field. Under the electric field, NOM rejection was increased because electrophoresis decreased the NOM concentration on the membrane surface. Additionally, NOM rejection depended on the pore size of membrane, even if a high electric field was applied, so the pore sizes of membrane appeared to be another important factor affecting the rejection ratio. With regard to the flux increase, the fouling reduction, and the rejection ratio enhancement under the electric field, the proposed method is more suitable for hydrophobic NOM solution. Moreover, compared with the experiment of electrophoresis, the electrophoretic mobility of hydrophobic components is higher than that of hydrophilic ones, and a positive correlation between the electrophoretic mobility and the performance of electrically enhanced membrane filtration was recognized. Our experimental results showed that the electrically enhanced membrane filtration can handle hydrophobic components where electrophoretic velocity is faster. Under these conditions, the electric field enhanced filtration process improves the removal efficiency and the filtration flux obviously. Hydrophobic water could also increase the total volume of permeate than hydrophilic water. Consequently, the electric field enhanced filtration has great potential for rejection of NOM containing more hydrophobic components. Key words: Natural organic matter; NOM; Hydrophobicity; Electric enhanced membrane process; pore sizes目 錄 頁 次 第一章 前言..................................... 1 1.1 研究動機與目的.................................... 1 1.2 研究項目.......................................... 3 第二章 文獻回顧................................. 4 2.1 水中天然有機物.................................... 4 2.1.1 天然有機物的來源與組成....................... 4 2.1.2 水中天然有機物的性質與影響................... 5 2.2 DAX-8樹脂...........................................8 2.2.1 DAX-8樹指分離原理.............................8 2.2.2 DAX-8樹指分離應用.............................9 2.3 GFC分子量分離......................................11 2.3.1 分子量分離原理...............................11 2.3.2 GFC分離水中天然有機物........................12 2.4 薄膜處理程序...................................... 14 2.4.1 薄膜孔徑大小、材質與操作.....................14 2.4.2 薄膜在淨水工程之應用........................ 16 2.4.3 影響薄膜操作之因子.......................... 17 2.4.4 薄膜機構之阻力分析.......................... 22 2.4.5 減緩薄膜機構之方法.......................... 25 2.5 外加電場薄膜過濾程序.............................. 26 2.5.1外加電場薄膜過濾原理與應用...................26 2.5.2臨界電場理論.................................28 2.5.3操作變因之影響...............................29 2.5.4外加電場對去除率的影響.......................31 第三章 實驗設備與方法.......................... 33 3.1 實驗設計與流程.....................................33 3.2 實驗步驟與方法.....................................35 3.2.1 腐植質溶液之配製............................ 35 3.2.2 DAX-8分離設備與分離方法.....................35 3.2.3 親疏水性水樣導電度去除...................... 38 3.2.4 GFC分子量分離設備與方法.....................39 3.2.5 薄膜外加電場模組及實驗程序.................. 42 3.2.6 阻力串連模式分析............................ 45 3.3 水質分析設備及分析方法.............................46 3.3.1 總有機碳分析方法及設備...................... 46 3.3.2 紫外光與可見光光譜儀........................ 47 3.3.3 粒子界達電位量測............................ 47 3.3.4 薄膜材質帶電性分析.......................... 48 第四章 結果與討論.............................. 49 4.1 腐植質分離與特性...................................49 4.1.1 DAX-8分離腐植質.............................49 4.1.2 腐植質分子量分佈............................ 50 4.1.3 親疏水性水樣導電度降低程序.................. 52 4.1.4 腐植質電泳動特性............................ 55 4.2 薄膜過濾通量與相關操作因子關連性探討...............57 4.2.1 進流水親疏水特性對UF薄膜過濾之影響..........57 4.2.2 UF薄膜孔徑對過濾之影響......................61 4.2.3 外加電場對UF薄膜過濾之影響..................64 4.3 薄膜去除效率與相關操作因子關連性探討...............78 4.3.1 進流水親疏水特性對UF薄膜去除率之影響........78 4.3.2 薄膜孔徑對UF薄膜去除率之影響................81 4.3.3 外加電場對UF薄膜去除率之影響................82 4.3.4 外加電場對去除消毒副產物前驅物質之影響...... 89 4.4 薄膜積垢阻力分析...................................92 4.4.1 不同親疏水性水樣之阻力分析.................. 94 4.4.2 不同薄膜孔徑之阻力分析...................... 97 4.4.3 薄膜外加電場程序之阻力分析.................. 98 第五章 結論與建議............................. 101 5.1 結論..............................................101 5.2 建議..............................................104 第六章 參考文獻............................... 105 附錄............................................ 113 圖 目 錄 頁 次 圖2.1.1 DOMs之組成........................................5 圖2.2.1 膠體體積表示圖...................................12 圖2.4.1 薄膜分離示意圖...................................14 圖2.4.2 各種薄膜的選擇性.................................15 圖2.4.3 過濾方向示意圖...................................21 圖2.4.4 薄膜積垢形式.....................................24 圖2.5.1 薄膜外加電場設備圖...............................27 圖3.1.1 實驗設計流程圖...................................34 圖3.2.1 DAX-8樹脂分離設備圖..............................36 圖3.2.2 分子量分離設備圖............................... 40 圖3.2.3 外加電場薄膜程序設備圖..........................44 圖4.1.1 分子量標準品層析圖...............................51 圖4.1.2 分子量校正曲線...................................52 圖4.1.3 腐植質分子量分離.................................52 圖4.1.4 疏水性水樣分子量分佈.............................54 圖4.1.5 親水性水樣分子量分佈.............................55 圖4.1.6 各水樣在不同pH下之電泳動情形.....................56 圖4.1.7 各水樣在不同pH值下界達電位值.....................56 圖4.2.1 以純水過濾之通量.................................58 圖4.2.2 各水樣對50KDa薄膜通量之影響......................59 圖4.2.3 各水樣對100KDa薄膜通量之影響.....................60 圖4.2.4 各水樣對300KDa薄膜通量之影響.....................60 圖4.2.5 腐植質原樣在不同薄膜膜孔下之通量衰減情形.........62 圖4.2.6 以體積表示腐植質原樣在不同薄膜膜孔下之通量衰減情形62 圖4.2.7 疏水性水樣在不同薄膜膜孔下之通量衰減情形.........63 圖4.2.8 親水性水樣在不同薄膜膜孔下之通量衰減情形.........64 圖4.2.9 外加電場對腐植質原樣通量之影響(50KDa薄膜)........67 圖4.2.10 外加電場對腐植質原樣通量之影響(100KDa薄膜)......67 圖4.2.11 外加電場對腐植質原樣通量之影響(300KDa薄膜)......68 圖4.2.12 外加電場對疏水性水樣通量之影響(50KDa薄膜).......69 圖4.2.13 外加電場對疏水性水樣通量之影響(100KDa薄膜)......69 圖4.2.14 外加電場對疏水性水樣通量之影響(300KDa薄膜)......70 圖4.2.15 外加電場對親水性水樣通量之影響(50KDa薄膜).......71 圖4.2.16 外加電場對親水性水樣通量之影響(300KDa薄膜)......71 圖4.2.17 外加25V電壓對各水樣通量之影響(50KDa薄膜)....... 72 圖4.2.18 外加55V電壓對各水樣通量之影響(50KDa薄膜)....... 73 圖4.2.19 外加125V電壓對各水樣通量之影響(50KDa薄膜)...... 73 圖4.2.20 外加25V電壓對各水樣通量之影響(100KDa薄膜)...... 74 圖4.2.21 外加55V電壓對各水樣通量之影響(100KDa薄膜)..... .74 圖4.2.22 外加25V電壓對各水樣通量之影響(300KDa薄膜).... ..75 圖4.2.23 外加55V電壓對各水樣通量之影響(300KDa薄膜)...... 75 圖4.2.24 過濾5小時總濾液體積(50KDa薄膜)................. 77 圖4.2.25 過濾5小時總濾液體積(300KDa薄膜)............... .77 圖4.3.1 進流水親疏水特性對去除率的影響(50KDa薄膜)........80 圖4.3.2 進流水親疏水特性對去除率的影響(100KDa薄膜).......80 圖4.3.3 進流水親疏水特性對去除率的影響(300KDa薄膜).......81 圖4.3.4 各水樣在不同薄膜膜孔下之平均去除率...............82 圖4.3.5 外加電場的影響(50KDa薄膜)........................84 圖4.3.6 外加電場的影響(100KDa薄膜)...................... 84 圖4.3.7 外加電場的影響(300KDa薄膜).......................85 圖4.3.8 55V電壓下各水樣在不同薄膜膜孔下之去除率..........85 圖4.3.9 125V下各水樣在不同MWCO薄膜下之去除率............ 86 圖4.3.10 外加電場下各水樣淨出水量提升效率(50KDa薄膜).....88 圖4.3.11 外加電場下各水樣淨出水量提升效率(300KDa薄膜)....89 圖4.3.12 外加電場下各水樣之SUVA分析(50KDa薄膜)...........90 圖4.3.13 外加電場下各水樣之SUVA分析(100KDa薄膜)..........90 圖4.3.14 外加電場下各水樣之SUVA分析(300KDa薄膜)..........91 圖4.4.1 各水樣之阻力分析(50KDa薄膜)......................96 圖4.4.2 各水樣之阻力分析(100KDa薄膜).....................96 圖4.4.3 不同電場下腐植質原樣之阻力分析(50KDa薄膜)........99 圖4.4.4 不同電場下腐植質原樣之阻力分析(100KDa薄膜)...... 99 表 目 錄 頁 次 表 2.2.1 DAX-8特性......................................9 表2.4.1 水樣特性對薄膜積垢的影響.........................17 表3.2.1 薄膜基本特性......................................43 表4.1.1 腐植質分離性質....................................50 表4.1.2 去除導電度前後之水樣性質.........................54 表4.2.1 有效電場.........................................65 表4.2.2 臨界電場.........................................65 表4.3.1 薄膜外加電場程序於不同操作條件下之去除效率(%)....86 表4.4.1 不同水樣及膜孔操作下之阻力........................97 表4.4.2 不同電場作用下之阻力分析........................1001019304 bytesapplication/pdfen-US天然有機物親疏水性外加電場薄膜程序膜孔大小Natural organic matterNOMHydrophobicityElectric enhanced membrane processpore sizesthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/62664/1/ntu-94-R92541121-1.pdf