臺灣博碩士論文加值系統

本研究為應用浮除（Flotation）法來處理半導體業中之化學機械研磨（Chemical mechanical polishing, CMP）廢水。廢水中主要含有奈米級之矽氧化物懸浮微粒，其具有相當穩定分散的能力。目前大部分廠商多利用傳統之化學混凝/沈澱來處理，但普遍都有大量加藥的情形。因此，本研究將嘗試利用浮除法來處理之以探討其可行性。
由分散式空氣浮除法之實驗結果顯示：透過添加陽離子性界面活性劑及調整酸鹼值，將能得到良好的浮除效果，殘餘的濁度可達10 NTU以下。當添加陽粒子性界面活性劑當作捕集劑使用時，其能藉由靜電作用力吸附於微粒表面，使表面呈疏水性；再靠架橋作用凝聚微粒形成較大的粒子，而且界面活性劑能加強氣泡與微粒碰撞、附著的機會，而有利於浮除。
在溶解式空氣浮除法方面：除了添加界面活性劑外，並添加混凝劑（鋁鹽及鐵鹽）作為活化劑，來探討其對浮除的貢獻。由結果顯示：陽離子性界面活性劑的添加與DiAF有相同的反應機制，並且其將扮演著重要的角色；而添加活化劑僅能改變廢水中微粒的表面特性其對浮除的貢獻有限。另外，若混合添加界面活性劑及活化劑，將能減少藥劑的添加量，並且能得到良好的浮除效果。此外，當提高飽和壓力及迴流率等操作條件於本浮除系統中，將能促進浮除的反應動力，但並不影響最終的去除效果。
經由本研究的結果可知，浮除法將適用於處理化學機械研磨廢水；處理過後的廢水，可迴流至廠區內水處理系統加以回收再利用。

Chemical mechanical polishing (CMP) wastewater in semiconductor industry is characterized as extremely stable dispersion of nano-size silica. Currently, coagulation-flocculation and sedimentation processes are employed by most of the semiconductor manufacturers in Taiwan. The feasibility of flotation processes to treat the CMP wastewater is evaluated in this study.
Experimental results indicated that both dispersed air flotation (DiAF) and dissolved air flotation (DAF) performed satisfactorily. In the DiAF experiment, cationic surfactant and pH value significantly affected flotation efficiency. The residual turbidity of less than 10 NTU can be obtained. The surface of fine silica of CMP wastewater became hydrophobic as a result of the adsorption of cationic surfactant via electrostatic force. It was found that bridging effect brought about by cationic surfactant could also result in the formation of flocs.
For DAF experiments, besides addition of cationic surfactant, coagulants (alum and ferric salts) were also used as activator. Results showed that reaction mechanism was the same as the DiAF experiments. Cationic surfactant dominated the flotation behavior while activators only had limited contribution. The flotation kinetics can be enhanced with increasing saturation pressure and recycle ratio.
Flotation processes show much potential for the treatment and possible reuse of CMP wastewater.

中文摘要Ⅰ
英文摘要Ⅱ
致謝Ⅲ
目錄………………………………………………………………..….. Ⅳ
圖表索引……………………………………………………………… Ⅶ
第一章 緒 論1
第二章 理論基礎與文獻回顧2
2.1 化學機械研磨技術與廢水之簡介2
2.1.1化學機械研磨技術2
2.1.2化學機械研磨原理2
2.1.3化學研磨液4
2.1.4化學機械研磨廢水處理及回收再利用現況4
2.2 浮除法8
2.2.1浮除法之簡介8
2.2.2影響浮除之因素8
2.2.2-1酸鹼值 ……………………………………………8
2.2.2-2浮除試劑…………………………………………..9
2.2.2-3起泡的產生………………………………………..9
2.3 界面化學15
2.3.1界面活性劑之定義與分類15
2.3.2界面活性劑之基本性質15
2.3.3界面活性劑應用在二氧化矽之浮選程序16
2.3.3-1界面活性劑應用在礦石表面之吸附行為16
2.3.3-2有關二氧化矽在浮除過程中氣/液/固三相
之機制.19
第三章 實驗設備與方法22
3.1 實驗材料22
3.2 實驗藥品22
3.3 實驗設備與裝置23
3.3.1分散式空氣浮除裝置……………………………………24
3.3.2溶解式空氣浮除裝置25
3.4 實驗項目與步驟29
3.4.1分散式空氣浮除實驗…………………………………….29
3.4.1-1不添加任何試劑浮除試驗………………………29
3.4.1-2添加捕集劑之浮除試驗30
3.4.2溶解式空氣浮除實驗…………………………………….31
3.4.2-1不添加任何試劑浮除試驗………………………31
3.4.2-2添加試劑之浮除試驗32
3.5分析方法33
3.5.1濁度分析33
3.5.2界達電位分析33
3.5.3紫外光/可見光光譜分析34
3.5.4總固體濃度及懸浮固體濃度分析……………………….34
3.5.5氨氮分析………………………………………………….34
3.5.6總有機碳分析…………………………………………….34
3.5.7粒徑分佈分析…………………………………………….35
3.5.8光學顯微照相…………………………………………….36
3.5.9元素分析36
第四章 結果與討論37
4.1 水質分析37
4.2 分散式空氣浮除實驗42
4.2.1不添加藥劑之浮除試驗42
4.2.2氣體流率對浮除動力學之探討………………………….43
4.2.3添加界面活性劑對浮除效率之影響45
4.2.3-1不同界面活性劑之影響45
4.2.3-2界面活性劑濃度之影響47
4.2.3-3酸鹼值之影響52
4.3 溶解式空氣浮除實驗67
4.3.1不添加藥劑之浮除試驗67
4.3.2飽和壓力對浮除效果之影響…………………………….69
4.3.3迴流率對浮除效果之影響……………………………….69
4.3.4添加界面活性劑對浮除效果之影響…………………….71
4.3.4-1不同界面活性劑之影響…………………………71
4.3.4-2界面活性劑濃度之影響…………………………71
4.3.4-3 酸鹼值之影響………………………………...…73
4.3.5添加活化劑對浮除效果之影響………………………… 74
4.3.6混合添加活化劑及界面活性劑對浮除效果的影響75
第五章 結論與建議……………………………………………………93
參考文獻……………………………………………………………… .96
附錄……………………………………………………………………107
符號說明………………………………………………………………118
作者簡介………………………………………………………………119

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