以聚電解質絮凝半導體廠廢水氟化鈣之研究｜國立臺灣科技大學博碩士論文系統

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研究生：	卓靖強 CHING-CHIANG CHO
論文名稱：	以聚電解質絮凝半導體廠廢水氟化鈣之研究 A Study on Flocculation of Calcium Fluoride Precipitates from Semiconductor Wastewater
指導教授：	劉志成 Jhy-Chern Liu
口試委員:	顧洋 Young Ku 黃志彬 Chih-Pin Huang 李篤中 Duu-Jung Lee 楊金鐘 Gordon C. C. Yang
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2007
畢業學年度：	95
語文別：	中文
論文頁數：	105
中文關鍵詞：	氟化鈣、含氟廢水、半導體、絮凝、雙重絮凝、聚電解質、膠羽破碎、膠羽回復
外文關鍵詞：	calcium fluoride, floc breakage, floc reformation
相關次數：	點閱：179 下載：0
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本研究主要目的在於探討以實廠半導體含氟廢水以固定鈣氟比為0.7，酸鹼值為7.5下將氟離子沉澱，形成氟化鈣懸浮液後，加入單一聚電解質或雙重聚電解質絮凝。比較不同分子量、加藥量及不同搭配下的絮凝系統其殘餘濁度的差異，並在絮凝時以光學散射分析儀PDA2000或小角度光散射儀線上監控膠羽的成長、破碎及再回復。
結果顯示以較低分子量的聚丙烯酸(PAA)絮凝有較低的殘餘濁度，但分子量為400萬的高分子量聚丙烯酸對於濁度的移除效果不佳。以雙重絮凝，發現加入較高劑量分子量9萬的聚丙烯酸搭配低劑量較高分子量之聚電解質，較可有效達到濁度去除的效果。其中以分子量9萬的聚丙烯酸搭配分子量為400萬的兩性聚電解質T204下有較佳的固液分離效果，且對於增加T204加藥量下也不易使濁度惡化。
以小角度光散射儀線上監控絮凝動態，可發現在雙重絮凝下，增加較高分子量聚電解質的劑量比例，可使膠羽長得較大，較不易破碎，但破碎後也較不易回復。而利用聚丙烯酸搭配T204形成的膠羽會比聚丙烯酸搭配陽離子性聚電解質KP1200B較易碎但有較好的回復性。在加快慢混轉速下可限制膠羽成長的大小，增加膠羽與細小顆粒的碰撞，使細小微粒有較佳的補捉效過，因此與一般轉速慢混下相比有更低的殘餘濁度。

ABSTRACT
The major objective of this study was to investigate flocculation and dual flocculation of calcium fluoride suspension from fluoride-containing wastewater of semiconductor manufacturer. This experiment utilized calcium chloride(CaCl2) and molar ratio, [Ca2+/F-] , was 0.7 at pH of 7.5. Residual turbidity was the major parameter after flocculated by polyelectrolytes of different molecular weight、dosage and combinations. The growth, breakage, and reformation of flocs was recorded on-line by PDA2000 or Small-angle light scattering instrument.
Better flocculaion was found when using low molecular weight PAA(polyacrylic acid). Turbidity removal was not as effective when using high molecular weight PAA. In the dual flocculation systems, better results were found when using PAA with low molecular weight (90K) combined with amphoteric polyelectrolyte ,T204.
In dual flocculation systems, both flocs size and strength increased, but the recovery decreased with increasing ratio of high to low molecular weight polyelectrolytes. The flocs formed by using PAA combined with T204 were easier to be broken and reformed than those by PAA combined with cationic polyelectrolyte KP1200B. Efficiency of fine particles capture increased with decreasing flocs size , and resulted in lower residual turbidity.

目  錄

摘要..........................................................................I
Abstract.....................................................................II
致謝........................................................................III
目錄.........................................................................IV
圖目錄.......................................................................VI
表目錄.......................................................................IX
第一章 緒 論..................................................................1
第二章 理論基礎與文獻回顧.....................................................2
2.1半導體產業廢水.............................................................2
2.2國內外對於含氟廢水處理技術之發展...........................................3
2.3聚電解質絮凝劑.............................................................8
2.3.1聚電解質的特性...........................................................9
2.4絮凝機制..................................................................10
2.5絮凝程序..................................................................14
2.6雙重絮凝..................................................................16
2.7膠羽破碎與再回復..........................................................19
2.8光學散射分析儀(PDA2000)...................................................20
2.9利用線上絮凝監控系統量測膠羽強度與回復性..................................21
第三章 實驗設備與方法........................................................23
3.1實驗材料..................................................................23
3.2實驗藥品..................................................................23
3.3實驗設備與裝置............................................................25
3.4實驗項目與步驟............................................................27
3.4.1實驗流程................................................................27
3.4.2瓶杯試驗................................................................28
3.4.3線上監控絮凝試驗........................................................29
3.5分析測定方法..............................................................31
3.5.1濁度分析................................................................31
3.5.2介達電位分析............................................................31
3.5.3膠羽粒徑分析............................................................31
3.6樣品分析..................................................................32
3.6.1殘餘氟離子濃度分析......................................................32
3.6.2濁度測定................................................................32
3.6.3界達電位測定............................................................33
3.6.4膠羽粒徑分佈分析........................................................33
3.6.5電子顯微照相............................................................33
3.6.7結晶型態分析............................................................34
第四章 結果與討論............................................................35
4.1原水性質..................................................................35
4.2氟化鈣懸浮液性質..........................................................35
4.3以陰離子聚電解質絮凝實驗..................................................42
4.3.1不同分子量陰離子聚電解質絮凝的影響......................................42
4.4聚電解質雙重絮凝實驗......................................................50
4.5 PDA2000光散射分析儀系統線上監控絮凝實驗..................................61
4.6以小角度光散射儀系統線上監控絮凝實驗......................................67
   4.6.2膠羽的破碎及回復性...................................................68
第五章 結論與建議............................................................77
附錄.........................................................................80
參考文獻.....................................................................89
作者簡介....................................................................105


圖 目 錄

圖2-1  表示聚電解質會因為離子強度增加而捲曲圖................................10
圖2-2  聚電解質鏈的吸附模式圖................................................11
圖2-3  (a)聚電解質藉由架橋方式絮凝 (b)顆粒因為吸附過多的聚電解質而達穩態.....13
圖2-4  聚電解質電性補綴於顆粒表面圖..........................................14
圖2-5  單一聚電解質的混凝程序圖..............................................15
圖2-6  雙重聚電解質加藥絮凝程序圖............................................18
圖2-7  不同階段膠羽的大小代表的參數..........................................22
圖3-1  PDA2000/Mastersizer2000 線上監控絮凝程序..............................26
圖3-3  實驗流程圖............................................................37
圖4-1  氟化鈣顆粒以X光散射儀分析圖...........................................39
圖4-2  氟化鈣顆粒以FESEM/EDS分析圖...........................................40
圖4-3  鈣氟比0.7、pH=7.5±0.02，以小角度光散射儀測量氟化鈣懸浮液粒徑圖........41
圖4-4  利用不同分子量的PAA絮凝氟化鈣懸浮液之介達電位圖.......................46
圖4-5  鈣氟比0.7、pH=7.5±0.02，以PAA(M.W.=90,000)絮凝氟化鈣顆粒之膠羽體積與數
量百分率粒徑分佈圖...........................................................47
圖4-6  鈣氟比0.7、pH=7.5±0.02，以PAA(M.W.=450,000)絮凝氟化鈣顆粒之膠羽體積與數量百分率粒徑分佈圖...........................................................48
圖4-7  鈣氟比0.7、pH=7.5±0.02，以PAA(M.W.=4,000,000)絮凝氟化鈣顆粒之膠羽體積與數量百分率粒徑分佈圖.........................................................49
圖4-8  利用PAA(M.W.=90,000)搭配KP1200B雙重絮凝氟化鈣懸浮液之殘餘濁度圖.......55
圖4-9  利用PAA(M.W.=90,000)搭配KP1200B雙重絮凝氟化鈣懸浮液之介達電位圖.......55
圖4-10 利用PAA(M.W.=90,000)搭配T204雙重絮凝氟化鈣懸浮液之殘餘濁度圖..........56
圖4-11 利用PAA(M.W.=90,000)搭配T204雙重絮凝氟化鈣懸浮液之介達電位圖..........56
圖4-12 利用PAA(M.W.=90,000)搭配PAM雙重絮凝氟化鈣懸浮液之殘餘濁度圖...........57
圖4-13 利用PAA(M.W.=90,000)搭配PAM雙重絮凝氟化鈣懸浮液之介達電位圖...........57
圖4-14 利用PAA(M.W.=90,000)搭配KP1200B雙重絮凝氟化鈣懸浮液之體積百分率中位數粒
徑圖.........................................................................58
圖4-15 利用PAA(M.W.=90,000)搭配KP1200B雙重絮凝氟化鈣懸浮液之數量百分率中位數粒徑圖.........................................................................58
圖4-16 利用PAA(M.W.=90,000)搭配T204雙重絮凝氟化鈣懸浮液之體積百分率中位數粒徑圖...........................................................................59
圖4-17 利用PAA(M.W.=90,000)搭配T204雙重絮凝氟化鈣懸浮液之數量百分率中位數粒徑圖...........................................................................59
圖4-18 利用PAA(M.W.=90,000)搭配PAM雙重絮凝氟化鈣懸浮液之體積百分率中位數粒徑圖...........................................................................60
圖4-19 利用PAA(M.W.=90,000)搭配KP1200B雙重絮凝氟化鈣懸浮液之數量百分率中位數粒徑圖.........................................................................60
圖4-20 在PDA2000系統以較低加藥量之單一絮凝動態圖.............................63
圖4-21 在PDA2000系統以較高加藥量之PAA(M.W.=90,000)單一絮凝動態圖.............64
圖4-22 在PDA2000系統以較高加藥量之PAA(M.W.=450,000)單一絮凝動態圖............64
圖4-23 在PDA2000系統以較高加藥量之PAA(M.W.=4,000,000)單一絮凝動態圖..........65
圖4-24 在PDA2000系統以較低加藥量之雙重絮凝動態圖.............................65
圖4-25 在PDA2000系統以較高加藥量之雙重絮凝動態圖.............................66
圖4-26 以20mg/L之PAA搭配3mg/L KP1200B在慢混150rpm及破碎轉速400rpm的PDA2000絮凝動態圖.......................................................................66
圖4-27 在小角度光散射儀係統以單一高分子絮凝之粒徑對時間關係圖................71
圖4-28 在小角度光散射儀係統以20mg/L分子量9萬PAA搭配KP1200B雙重絮凝之粒徑對時間關係圖.......................................................................72
圖4-29 在小角度光散射儀係統以30mg/L分子量9萬PAA搭配KP1200B雙重絮凝之粒徑對時間關係圖.......................................................................72
圖4-30 在小角度光散射儀係統以20mg/L分子量9萬PAA搭配T204雙重絮凝之粒徑對時間關係圖...........................................................................73
圖4-31 在小角度光散射儀係統以30mg/L分子量9萬PAA搭配T204雙重絮凝之粒徑對時間關係圖...........................................................................73
圖5-1  慢混以100rpm，破碎300rpm剪力下的PDA2000系統絮凝動態圖.................79
圖5-2  慢混以100rpm，破碎300rpm剪力下的小角度光散射儀系統絮凝動態圖..........78


表 目 錄

表3-1  表3-1聚電解質特性.....................................................24
表4-1  由ICP測量實廠含氟廢水溶液中元素表.....................................38
表4-2  實廠含氟廢水基本性質..................................................38
表4-3  氟化鈣懸浮水樣基本性質................................................38
表4-4  含氟溶液以鈣鹽及不同濃度 PAA(M.W.=90,000)之處理效果...................45
表4-5  含氟溶液以鈣鹽及不同濃度 PAA(M.W.=450,000)之處理效果..................45
表4-6  含氟溶液以鈣鹽及不同濃度 PAA(M.W.=4,000,000)之處理效果................46
表4-7  含氟溶液以鈣鹽及固定濃度PAA(M.W.=90,000) 搭配不同濃度KP-1200B之處理效果...........................................................................52
表4-8 含氟溶液以鈣鹽及固定濃度PAA(M.W.=90,000) 搭配不同濃度T-204之處理效果...53
表4-9  含氟溶液以鈣鹽及固定濃度PAA(M.W.=90,000)搭配不同濃度PAM之處理效果.....54
表4-10 在PDA2000系統以較低加藥量之單一絮凝之破碎與回復率.....................63
表4-11 由小角度光散射儀系統動態絮凝圖所得破碎率與回復率表....................74
表4-12 由PDA2000系統在一般絮凝及小角度光散射儀系統在加快慢混轉速絮凝後濁度比較表...........................................................................76

                                

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