臺灣博碩士論文加值系統

聚氯化鋁(PACl)廣泛用於工業廢水處理或飲用水淨化，包括在聚氯化鋁中的聚合鋁或高價鋁物種（Al13，[AlO4Al12(OH)24(H2O)12]7+)可以抵抗溶液中的背景離子干擾及直接與粒子作用電性中和反應。
因此，許多學者致力於研究PACl中鋁物種的成份。本研究主要目的是探討兩種製備PACl方式間鋁水解產物的差異，這兩種方式是將非定型的氫氧化鋁加酸處理形成之PAClacid和將氯化鋁溶液以傳統加鹼處理形成之PAClbasic，而這兩種製備PACl方式幾乎完全不同，所製備出的PACl成份理論上應該差異很大。
根據Al-Ferron分析得知於0.1M下不同B值的PAClacid及PAClbasic所形成之鋁型態分佈趨勢相近，然而，PAClacid及PAClbasic之Alb及Al13的比值卻有所差異，顯示PAClbasic所形成的Alb幾乎全為Al13，而PAClacid中除了Al13還有其他鋁物種，因此，根據Al-Ferron逐時螯合比色法和27Al核磁共振法分析之結果，雖然加酸法與加鹼法皆可形成聚合鋁(Alb)，但其聚合物中的Alb並非相同。
在此研究中也發現PAClacid的鋁物種受時間及溫度的影響較PAClbasic明顯，因此，為了探討PAClacid及PAClbasic成份中的分子差異以瞭解此現象的原因，本研究將利用不同孔徑(1、3、5kD)超濾膜探討不同B值製備PAClacid及PAClbasic中成份分佈的差異性，透過各濾紙的截留率證實B值2.3的PAClacid比PAClbasic平均分子量還要大。此外，利用瓶杯試驗之殘留濁度可以發現當在分子量3kD以上之成份確實較能看出差異性，特別是B值2.3的PAClacid平均分子量明顯高於Al13，可能以Al30分子存在，結果顯示在高B值時兩種製備方式的鋁物種分子大小分佈確實有很大差異。

Polyaluminum Chloride (PACl) is broadly used for treating industrial wastewater or purifying drinking water. Including in the PACl, the polymeric aluminum or high valance aluminum species (i.e.Al13 species, [AlO4Al12(OH)24(H2O)12]7+) can resist the interferences of the background ions in the solution and directly react with the particles in the solution to neutralize the electron charge of particles.
Therefore, many scholars have dedicated to studying about the components of Al species in polyaluminium chloride.The main objective of this research was studying the differences of aluminum hydrolytic products between two PACl preparation methods. These two methods were the acidification process of freshly formed amorphous Al(OH)3 to form PAClacid and the conventional alkalization process of aluminum chloride solution to form PAClbasic.This two PACl preparation methods are completely different, in theoretical the PACl composition should also be difference.
According to Al-Ferron analysiswe found that the distribution of the aluminum forms was similar by PAClacid and PAClbasic at different Basic values (B) under 0.1 M condition. However, the Alb/Al13 ratio of PAClacid and PAClbasic is different, showing the Alb of PAClbasic almost all Al13, and there are other aluminum species except Al13 in the PAClacid. Therefore, according to the results of Ferron test and 27Al NMR analysis, although the Alb can be produced in both acid and alkaline addition method, the polymeric species of Alb are not similar.
In this study, it was also found that PAClacid aluminum species were more obviously affected by time and temperature than PAClbasic done. Therefore, in order to investigate the different molecular in PAClacid and PAClbasic then further understand the causes of above phenomenon. In this study we use the ultrafiltration membranes (pore size1、3、5 kD)to investigate the composition difference between PAClacid and PAClbasic at different B values. Through the membrane filtration rate, it proved that PAClacid at B=2.3has greater average molecular weight than PAClbasic.Furthermore, using residual turbidity in Jar test it can be figure out while the molecular weight above 3kD can certainly see the difference between PAClacid and PAClbasic, especially the PAClacid at B=2.3 which average molecular weight is obviously higher than that of Al13.It may be caused by the PAClacid exist ofAl30 molecules in this B values. The results showed that the molecular size distribution of the aluminum species in both preparing methods were suspected to be significantly different at high Basicity value.

誌謝 I
摘要 II
Abstract IV
目錄 VII
圖目錄 XII
表目錄 XV
第一章緒論 1
1.1研究緣起 1
1.2研究目的 2
第二章文獻回顧 4
2.1聚氯化鋁之混凝特性 4
2.1.1混凝之理論 4
2.1.2混凝劑 9
2.1.3聚氯化鋁 10
2.1.4聚氯化鋁的化學性質與混凝機制 11
2.2鋁的水解化學 13
2.2.1鋁的水解聚合特性 13
2.2.2聚合鋁物種生成機制 17
2.2.3Al13穩定特性分析 22
2.2.4Al13之生成機制 23
2.2.5Al30生成機制之特性 26
2.3鋁分子大小分佈 29
2.3.1膠凝過濾層析法 29
2.3.2超濾膜過濾法 29
2.4鋁型態分析方法 33
2.4.1Al-Ferron逐時螯合比色法 34
2.4.2 27Al NMR核磁共振法 36
2.4.3原子吸收光譜法 38
2.5混凝效果的評估方法 39
2.5.1傳統瓶杯試驗 39
2.5.2線上型連續濁度偵測系統 40
第三章材料與方法 43
3.1研究架構 43
3.2實驗流程 45
3.2.1實驗藥品 48
3.2.2實驗器材設備 50
3.3實驗方法 53
3.3.1微量加酸法製備聚氯化鋁 53
3.3.2微量加鹼法製備聚氯化鋁 54
3.4鋁分子大小分佈 55
3.4.1液相聚合物截留 55
3.5混凝評估差異之方法 59
3.5.1傳統混凝之瓶杯試驗 59
3.5.2光學式濁度分析 60
3.6鋁分析方法 63
3.6.1 Al-Ferron逐時螯合比色法 63
3.6.2 火焰式原子吸收光譜儀 63
第四章結果與討論 65
4.1以不同條件製備PACl方式探討鋁型態分佈 65
4.1.1微量加鹼及微量加酸法在不同濃度下鋁型態分佈 65
4.1.2微量加鹼及加酸法製備PACl之Al13及Alb比值分佈差異 69
4.1.3老化時間對不同B值微量加鹼及加酸法之鋁物種的影響性 71
4.1.4老化溫度對不同B值微量加鹼及加酸法之鋁物種的影響性 74
4.2以超濾膜過濾法探討不同製備PACl方式之差異性 77
4.2.1以不同孔徑超濾膜進行過濾時濾液體積與過濾時間之相關性 77
4.2.2老化溫度與濾速之相關性 81
4.2.3老化時間與濾速之相關性 84
4.2.4不同製備方式鹼化程度之PACl分子量分佈情況 87
4.2.5鋁型態與濾紙截留鋁量的關係 88
4.2.6各濾紙的截留率 89
4.3以瓶杯試驗探討不同B值製備PACl方式之差異性 91
4.3.1不同B值製備方式混凝劑之劑量對混凝殘餘濁度變化 91
4.3.2不同製備方式及B值混凝劑，混凝靜置時間之濁度變化 92
4.4以線上型濁度分析探討不同B值製備PACl方式之差異性 98
4.4.1不同製備方式及B值混凝劑過濾前/後線上連續濁度偵測變化 98
4.4.2 不同製備方式混凝劑過過濾後之標準偏差值 103
第五章結論與建議 104
5.1結論 104
5.2建議 106
參考文獻 107

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