[[alternative]]Metal-chelating character of wastewater generated from metal-complex dye manufacturing processes : using chelated iron concentration to evaluate the removal efficiency of chelating functional group and treatment options

碩士[[abstract]]研究中所談之染料製程廢水，為染料製程廢水為在染料之製作過程中所排放，其中含有合成此種染料所必須加入之各種化學物質，以及經過調整酸鹼度或溫度等程序，因此製程廢水應含有許多合成染料之過程中所產生的過渡化合物，並且除了含有結構較完整之染料分子，還有一些還未完成染料分子之單體結構。 混凝處理後，有機物去除效率不佳，且當pH值越低，其色度越高，測溶解鐵後發現廢水具有螯合金屬的能力。而後再以已形成之氫氧化鐵吸附有機物，有機物的去除效率也不佳。因此廢水混凝效果不佳的因應為廢水本身大部分為親水性較佳之有機物。 螯合金屬則為屬絡合染料製程廢水之特性，以C/Fe3+顯示處理後螯合之官能基之破壞情形。原水之C/Fe3+=15，生物處理後C/Fe3+=29，過硫酸鹽加熱後C/Fe3+=13，由此可知經由生物處理後，能破壞大部分之螯合金屬的官能基，且TOC也去除一半以上，因此生物處理可作為廢水之前處理，再結合其他處理程序。 本研究之處理方式為利用類似於Homogeneous Fenton-like，為亞鐵離子與廢水中螯合金屬之官能基螯合，亞鐵離子能因被螯合而呈溶解態，均勻地分布於廢水中，並能於中性時反應。因此實驗進行於pH7，並與進行於pH3比較。實驗結果為過氧化氫於pH3與pH7下，其隨時間之消耗量相同，但有機物與色度去除率於pH3時較佳 ，而於pH7時也能夠去除少部分之有機物(pH3之TOC去除率約20%，pH7約為5%；色度於pH3時去除率約70%，pH7時去除率約10%)。於pH7時，未被螯合之亞鐵離子逐漸氧化成三價鐵離子，一部分與過氧化氫形成錯合物 (Fe2O3．nH2O)沉澱，一部分則與氫氧根離子結合，形成氫氧化鐵沉澱，則無法再進入Fenton反應之循環中。因此要使用Homogeneous Fenton-like之方法處理時，應考慮能螯合亞鐵離子的量，使較多之亞鐵離子被螯合後，則不受到pH值之影響。[[abstract]]In this study, Dye manufacturing processes wastewater (DMPW) is the effluent generated from synthesizing process of dyes, consisting of intermediated compounds, monomer structure, and dyes molecules. Coagulation is found to be an inefficient process for removing organic matters. Color of treated water is increased with the decreasing coagulation pH. Measured dissolved iron after coagulation allowed one to evaluate the content of functional groups of organics which can chelate iron from coagulant. Organic removal efficiency is also not very well when pre-precipitated ferric hydroxide was used as adsorbent. It is concluded that DMPW contains hydrophilic functional groups as the result that coagulation is not able to remove the most of the organic matters. One feature of DMPW is its metal-chelating ability. The C/chelated-Fe3+ molar ratio is used to explore the destruction of chelating functional groups after various treatment processes. The C/chelated-Fe3+ molar ratios of raw DMPW, biologically- treated DMPW, and thermo-persulfate treated DMPW are 15, 29, and 13, respectively. Since chelating functional groups and TOC were reduced after biological treatment, biological treatment process can be employed as a pretreatment process to improve degradation efficiency of DMPW. In this study, the chelating characteristic of DMPW was exploited with Homogeneous Fenton-like process being tested. The potential of chelating functional groups to enhance oxidation efficient in the Fe(III)/H2O2 system under neutral pH condition was compared with the same process at pH 3. Our results show that the trend of residual hydrogen peroxide concentration in neutral and acidic pHs were the same during a 3-hr reaction. A higher degree of organic matters and colour removal were observed at pH3. The removal efficiencies of TOC are 20% and 5% under pH 3 and pH 7 conditions, respectively, while the removal efficiencies of color are 70% and 10%, respectively. Under pH 7 condition, unchelated ferrous ions are oxidized to ferric ions gradually, and ferric ions form complexes (Fe2O3．nH2O) and precipitate as ferric hydroxide. The precipitated ferric ions could not be used efficiently in Fenton cycle.[[tableofcontents]]目錄 目錄 I List of Figure IV List of Table VII 第一章 序論 1 1.1研究之背景及目的 1 1.1.1研究緣由 1 1.1.2研究之目的 3 第二章 文獻回顧 4 2.1 金屬絡合染料 4 2.1.1 金屬絡合原理 4 2.1.2金屬絡合染料用途 6 2.1.3金屬絡合染料之處理研究 6 2.2混凝機制與處理染料之研究 13 2.2.1 混凝 13 2.2.2 混凝劑之種類及使用時機 14 2.2.3混凝程序處理染料之研究 14 2.3 高級氧化處理程序(AOP)機制與處理染料之研究 16 2.3.1 Fenton 16 2.3.2 過硫酸鹽 (Persulfate , S2O82-) 18 2.3.3 Homogeneous Fenton-like 19 2.4 連續接觸式曝氣法 22 第三章 實驗材料設備與方法 23 3.1實驗流程 23 3.2實驗材料與設備 24 3.2.1實驗試劑 24 3.2.2實驗設備 27 3.3分析方法 28 3.3.1總鐵離子量測方法 28 3.3.2亞鐵離子量測方法 29 3.3.3過氧化氫量測方法 30 3.3.4水中化學需氧量檢測方法 31 3.3.5水中生物化學需氧量檢測方法 32 3.3.6水中溶氧檢測方法 33 3.4研究主題分述 34 3. 4.1金屬絡合染料製程廢水之原水混凝 34 3. 4.2預形成之Fe(OH)3吸附染料製程廢水 34 3. 4.3金屬絡合染料製程廢水特性實驗-原水 35 3. 4.4金屬絡合染料製程廢水特性實驗-Persulfate加熱 36 3. 4.5金屬絡合染料製程廢水特性實驗-連續接觸式曝氣法 36 3. 4.6 Homogeneous Fenton-like 38 第四章 結果與討論 42 4.1金屬絡合染料製程廢水之原水混凝與特性 42 4.1.1ADMI及COD去除效率 42 4.1.2混凝後之溶解態鐵量 44 4.1.3氫氧化鐵吸附試驗 46 4.2金屬絡合染料製程廢水特性 49 4.2.1金屬絡合染料製程廢水原水特性 49 4.2.2染料製程廢水經生物處理後之特性 53 4.2.3染料製程廢水經Persulfate加熱後之特性 55 4.3金屬絡合染料製程廢水之處理方法探討-Homogeneous Fenton-like 58 4.3.1金屬絡合染料製程廢水之螯合亞鐵離子 58 4.3.2 金屬絡合染料製程廢水處理方法探討-Fenton/ Homogenous Fenton-like 61 第五章 結論 65 5.1結論 65 5.1.1混凝與氫氧化鐵吸附 65 5.1.2特性探討 66 5.1.3 依特性之處理方法探討 67 5.2建議 68 5.2.1混凝與氫氧化鐵吸附 68 5.2.2特性探討 68 5.2.3依特性之處理方法探討 68 Reference 70 List of Figure Figure 1. Chemical structure of the metal complex dyes：A. The Neutral Blue BNL,C20H15N5O5S.Cu, 500.79g/mole. B. The Neutral Pink BL, C32H24N12O12S2.Cr.Na, 907.79 g/mole. Adapted from [25]. 4 Figure 2. Experiment process 23 Figure 3. The calibration curve of Fe concentration measured by an atomic absorption spectrometer. 28 Figure 4. The calibration curve of Fe2+ concentration measured by UV-Vis Spectrophotometer. 30 Figure 5. The calibration curve of H2O2 concentration measured by UV-Vis Spectrophotometer. 31 Figure 6. The contact aerator. 37 Figure 7. The experimental flow chart of Homogeneous Fenton-like and Fenton treatment process. 41 Figure 8. The effect of ADMI and COD on coagulation with 500 and 1000 mg/L Fe3+ under various pH. Error bars represent the standard deviation of triplicate experiments. 43 Figure 9. Dissolved Fe3+ concentration as a function of pH 3~ 7 for 500 and 1000 mg/L as Fe3+ and in DMPW and DI water. Error bars represent the standard deviation of triplicate experiments. 45 Figure 10. COD removal as Fe3+ precipitated for 500mg/L and 1000mg/L Fe3+ added after coagulation in pH3~7. Error bars represent the standard deviation of triplicate experiments. 46 Figure 11. TOC (mg/L) and ADMI as Fe(OH)3 (mg/L) added under pH7. 48 Figure 12. TOC (mg/L) and ADMI as coagulation and adsorption process. 49 Figure 12. Dissolved Fe3+ concentration as a function of Fe3+ added as various TOC concentrations in 3151, 2368, 1579, 789, 0 mg/L DMPW. Error bars represent the standard deviation of triplicate experiments. 51 Figure 13. Dissolved Fe3+ concentration as a function of TOC for the saturating dissolved Fe3+ in multiple concentrations of dye. Error bars represent the standard deviation of triplicate experiments. 52 Figure 14. Dissolved Fe3+ -mmole/L as a function of C-mmole/L for the saturating dissolved Fe3+ in multiple concentrations of dye. Error bars represent the standard deviation of triplicate experiments. 52 Figure 15. Dissolved Fe3+ concentration after biological treatment as a function of Fe3+ added as various TOC concentrations in 618, 464, 309, 155 mg/L DMPW. Error bars represent the standard deviation of triplicate experiments. 54 Figure 16. Dissolved Fe3+ concentration as a function of TOC for the saturating dissolved Fe3+ in multiple concentrations of dye after biological treatment. 54 Figure 17. Dissolved Fe3+ -mmole/L as a function of C-mmole/L for the saturating dissolved Fe3+ in multiple concentrations of dye after biological treatment . 55 Figure 18. Dissolved iron concentration as a function of Fe3+ added under various sodium persulfate concentrations of 0, 500, 5000, 10000 mg/L heated in 90℃and 270 mins for treating 25%-diluted DMPW. Error bars represent the standard deviation of triplicate experiments. 56 Figure 19. Dissolved iron concentration as a function of Fe3+ added under various sodium persulfate concentrations of 0, 500, 5000, 10000 mg/L heated in 90℃and 270 mins for treating 25%-diluted DMPW. Error bars represent the standard deviation of triplicate experiments. 57 Figure 20. Dissolved Fe3+ -mmole/L as a function of C-mmole/L for the saturating dissolved Fe3+ in multiple concentrations of dye after AOP treatment (persulfate with heat) . 57 Figure 21. Chelated Fe2+concentration as a function of TOC for the chelating Fe2+ in 0.03mM for treating 10%-diluted DMPW. 59 Figure 22. Fe2+ chelated concentration as a function of TOC for the chelating Fe2+ in 0.03mM for treating 10%-diluted DMPW. 59 Figure 23. Chelated Fe2+ -mmole/L as a function of C-mmole/L for the chelating Fe2+ in 0.03mM for treating 10%-diluted DMPW. 60 Figure 24. Residual hydrogen peroxide concentration (mg/L) as various times (min). Error bars represent the standard deviation of triplicate experiments. 63 Figure 25. TOC, ADMI, and dissolved iron concentration after Fenton process. Error bars represent the standard deviation of triplicate experiments. 64 List of Table Table 1. Summary of the researches related to treatment of metal-complex dye. 6 Table 2. Operation condition and Characteristic of coagulants. Adapted from [30]. 14 Table 3. Some of the researches related to Fe(II)-media-oxygen. 20 Table 4. Materials need of this investigation. 24 Table 5. The characteristic experiments. 66 Table 6. Fe2+ chelated experiments. 67[[note]]學號: 600480080, 學年度: 10