臺灣博碩士論文加值系統

在水處理領域中，化學混凝為經常使用的處理程序，一般認為混凝劑之聚合程度會與混凝電性中和能力有關，以鋁鹽混凝劑為例，聚氯化鋁主要物種為Al13([AlO4Al12(OH)24(H2O)12]7+)，因在生產過程已經預水解，被認定在實際混凝程序中比Al3+離子有較好的穩定性，因此也具有較佳的電性中和能力。相反的雖然單核性Al3+混凝劑之水解速度過快，通常較不具穩定性而無法有效進行電性中和，但事實上混凝受原水鹼度和pH值之影響極大，Al13在低鹼度時會降低其電性中和能力，故是否須將混凝劑預水解至高鹼基值得到高Al13比之混凝劑，才能得到較佳的電性中和效果，值得探究。
腐植酸(Humic Acid, HA)為廣泛存在的天然有機物，常使用混凝程序將其去除，一般評估腐植酸與混凝劑電性中和的方式，通常是使用瓶杯試驗，界達電位等作為評估方式，但這些皆為間接式的評估方法，因此本研究將以腐植酸作為評估標的，利用腐植酸會與金屬離子形成錯合反應產生螢光效滅效應(Fluorescence quenching efficiencies)，以Stern-Volmer線性公式量化得到熄滅常數值(Kq)，以及利用錯合物形成滴定法，同時考慮腐植酸與金屬離子發生錯合鍵結過程中，H+離子及OH-離子形成副反應時之有效穩定常數(effective stability constant, K´MY)變化情況，評估混凝劑聚合程度對腐植酸在不同pH值及鹼度值條件下電性中和效果之差異性。
利用腐植酸添加不同鹼化度(Basicity, B=[OH]/[Al])的PACl下螢光熄滅現象，與改變溶液之pH值及PACl劑量條件下的實驗結果，(1)在酸性溶液時，不同B值PACl之Kq值比較為PACl-2.5>PACl-2.3>
PACl-1.5>AlCl3；(2)在鹼性溶液時，不同B值PACl之Kq值比較為PACl-1.5>PACl-2.3> PACl-2.5 >AlCl3；(3)在腐植酸溶液為pH=6的條件下，不同B值之PACl皆得到最大Kq值，表示此時腐植酸與PACl混凝較不受H+或OH-離子副反應影響，而有最佳的錯合反應或電性中和效果，因此本研究以Kq值作為判斷電性中和能力之方式是可行的，且相較於過去以表面電位作為間接判斷電性中和能力之方式，更能節省實驗的複雜性，並提供更精準的混凝反應常數。

In general, the electrical neutralization capacity of coagulant is affected by its polymerized status. For example, the main species of polyaluminum chloride is Al13 ([AlO4Al12(OH)24(H2O)12]7+), whose production process has occurred prehydrolysis phenomenon. It was reported that the polyaluminum chloride was more stable than Al3+ ions in an actual coagulation procedure. Therefore, the polyaluminum chloride performance to neutralize the electric charge of the suspended particles is better than that of the Al3+ ions. In the past, alkaline was added to increase the proportion of Al13. In contrast, mononuclear Al3+ coagulant hydrolysis was rapid and the coagulant was unstable in a coagulation process so that the electric charge of the particles could not be effectively neutralized. However, the coagulation process was greatly affected by basicity and pH value. Therefore, the electrical neutralization performance of Al13 was relatively poor in low basicity conditions.Hence, to produce good electrical neutralization coagulants, the subject of pre-hydrolysis process at high B value is worth to be studied.
Humic acid (HA) is a kind of natural organism, which can be widely removed by coagulation. Currently, Jar Test or Zeta Potential test are commonly used for the study of coagulant neutralizing the humic acid’s electric charges, but these are indirect evaluating methods. Hence, in this study, the humic acid will be the removal target, which using (1) Stern-Volmer linear equation will be used to obtain the constant value (Kq) of the fluorescence quenching efficiencies. Then, (2) a titration to form the humic-metal complex will be also conducted. According to the titration results, the effective stability constant (K’MY), which is determined from the side-reactions of both H+ and OH- ion generations in the humic-metal complex reaction, will also be studied. Through the above two “constant” studies are considered as the theoretical to evaluating its electrical neutralization efficiency under various conditions of pHs, coagulant dosages (Aluminum content percentages) and coagulant types.
The experimental results of fluorescence quenching effect on pH value of the solution and PACl dosagesin humic acid adding Polyaluminum Chloride with various B values (Basicity, B=[OH]/[Al]). (1) In acidic solution, compared of the Kq values of PACl with various B values are PACl-2.5>PACl-2.3>PACl-1.5>AlCl3; (2) In alkaline solution, compared of the Kq values of PACl with various B values are PACl-1.5>PACl-2.3>PACl-2.5>AlCl3; (3) Under the humic acid’s solution was pH=6, PACl of various B values are acquired the maximum Kq values. Indicating that PACl coagulation on humic acid is not affected by side-reactions of both H+ and OH- ion. Therefore, in this study, it is feasible to use the Kq value as a way to determine the ability of electrical neutralization, which can save the complexity of experiment and provide more accurate reaction constant than the past indirect way as surface potential.

致謝 I
摘要 II
Abstract IV
目錄 VII
圖目錄 XI
表目錄 XIV
第一章 前言 1
1.1研究緣起 1
1.2研究目的 3
第二章 文獻回顧 4
2.1聚氯化鋁混凝劑 4
2.1.1混凝機制 4
2.1.2 Al13的特徵 7
2.1.3聚氯化鋁的鋁型態分佈 8
2.14鋁的水解聚合特性 14
2.2混凝效果評估方法 17
2.2.1傳統瓶杯試驗(Jar test) 18
2.2.2界達電位 18
2.3 PACl與有機物之混凝作用 19
2.4天然有機物-腐植酸之來源與性質 20
2.5螢光熄滅常數 23
2.6錯合物形成滴定法 24
第三章 研究方法 28
3.1 研究架構 28
3.2實驗流程 30
3.3腐植酸原液配製 32
3.4聚氯化鋁製備 32
3.5 Al-Ferron逐時螯合比色法 34
3.6評估方法 36
3.6.1螢光光譜儀 36
3.6.2濁度計 37
3.6.3紫外光光譜儀 37
第四章 結果與討論 38
4.1以螢光熄滅現象探討腐植酸與PACl混凝後電性中和能 38
4.1.1不同腐植酸濃度與螢光強度之關係 38
4.1.2添加不同濃度氯化鋁後腐植酸螢光強度改變 39
4.1.3探討腐植酸添加不同B值PACl下螢光熄滅現象與溶液 之pH值及PACl劑量之相關性 40
4.1.4利用螢光熄滅常數探討不同B值PACl電性中和能力之 差異性 51
4.1.5不同製備方式之PACl對腐植酸電性中和能力之差異 55
4.1.6以螢光熄滅率探討PACl適用範圍 57
4.2由濁度改變觀察PACl對腐植酸電性中和能力差異性 59
4.2.1比較不同製備方式PACl與腐植酸混凝後濁度變化 59
4.2.2腐植酸與不同B值PACl混凝後濁度變化 64
4.3利用UV254值變化及螢光熄滅現象比較PACl電性中和能力差異性 66
4.3.1不同腐植酸濃度與UV254值之關係 66
4.3.2不同pH值下腐植酸過濾前後UV254值差異 67
4.3.3腐植酸與不同B值PACl混凝後UV254去除率之差 68
4.3.4腐植酸在不同pH條件下UV254值變化 69
4.3.5以UV254去除率及螢光熄滅率比較PACl電性中和能力差異性 71
第五章 結論與建議 73
5.1結論 73
5.2建議 75
參考文獻 76

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