電路板產業是三大零件製造業之一，為用水需求極高的產業，製造過程會排出大量重金屬廢水，如未經適當處理，可能會間接造成人體危害。
有研究發現於pH>9.25時，利用低亞硫酸鈉可將含氨與銅離子之水中將銅還原為零價銅顆粒，去除率可達99%，作者認為氨存在是必要的，能與銅螯合為銅氨形式，最後還原為零價銅顆粒。本研究利用MINEQL+ 化學平衡軟體模擬含氨與銅離子之化學物種，發現銅在低pH下以離子形式存在，不會與氨螯合，在pH6- pH10少部分與NH3螯合，大部分以氫氧化銅形式存在，顯示銅與氨螯合效果不佳。因此，本研究先探討氨存在的必要性，並欲利用原本廢水中含有EDTA的特性，代替以低亞硫酸鈉做化學還原法去除銅所需要的氨。
實驗結果顯示，高pH時氨會變為氣態，逸散回空氣中，無法有效與銅螯合，造成去除率下降，長時間反應雖有高去除率，但以氫氧化銅形式被去除，如以曝氮氣方式，能有效防止氫氧化銅產生。在低pH下無氨水螯合時，低亞硫酸鈉也能將銅離子還原為銅顆粒，顯示還原過程氨水並非必要存在。以低亞硫酸鈉還原EDTA-Cu廢水，在pH3- pH11皆能有效將銅離子還原為銅顆粒，去除率達80%以上。EDTA系統長時間攪拌後以顆粒形式存在，與氨系統中氫氧化銅形式不同。

Printed Circuit Board is one of the three major electronic parts manufacturing industries. The manufacturing of PCB consumes a lot of water and produces enormous heavy metal-containing wastewater. Without appropriate treatment wastewater will cause great damage to human health.
The literature shows that Cu ion could be reduced to Cu atom by sodium dithionite and removed from water with removal rate of 99% at pH>9.25. According to these authors, NH3 played a key role in the reduction process by chelating with Cu ion to form [(Cu(NH3)4)]2+ . In this research, we use MINEQL+ (chemical equilibrium software) to simulate the chelation between Cu ion and NH3. The simulation indicates that Cu ion doesn’t chelate NH3 at low pH value and most of Cu ions are in the form of Cu(OH)2 at pH6-10. Fraction of [(Cu(NH3)4)]2+ species is very tiny at pH>9.25, therefore, the significance of NH3 in Cu reduction needs to be verified. Meanwhile, if chelation of copper is important in copper reduction, EDTA which is ubiquitous in PCB wastewater might play the same role as NH3, and the effect of EDTA on copper reduction is also investigated.
Experimental results show that at high pH value NH3 molecules vaporize into gas phase, Cu ion doesn’t chelate NH3 and cause lower removal rate. After a long time, the removal rate recovered due to formation and precipitation of Cu(OH)2. Nitrogen purging can effectively prevent formation of Cu(OH)2. At low pH value without ammonium ligand, Cu ion could be reduced to Cu atom by sodium dithionite, which indicated NH3 is not essential in reduction. The reduction of Cu ion to metallic Cu in EDTA-Cu water by sodium dithionite could happen efficiently at pH3-11 at reaction time of 30 min.

目錄
圖目錄	IV
表目錄	VIII
第一章、前言	1
1-1 研究緣起	1
1-2 研究目的	2
第二章、文獻回顧	3
2-1 銅	3
2-2 螯合作用	5
2-2-1 螯合之形成	5
2-2-2 常見螯合劑	5
2-3 傳統重金屬去除技術	9
2-3-1 重金屬去除技術之優缺點	12
2-3-2 事業廢汙水排放標準	13
2-4 低亞硫酸鈉(Na2S2O4)	14
2-4-1 化學還原法將銅離子還原為銅原子	15
第三章、實驗材料與方法	17
3-1 實驗材料與設備	17
3-1-1 實驗藥品與材料	17
3-1-2人工含銅廢水及儲備液製備	18
3-1-3 實驗設備	18
3-2 實驗分析方法	19
3-2-1 銅固體分析	19
3-2-2 銅離子之分析	20
3-3 實驗步驟	20
3-3-1 實驗流程圖	20
3-3-2 實驗流程	21
3-4 低亞硫酸鈉(Na2S2O4)之穩定性測試	23
3-4-1 低亞硫酸鈉(Na2S2O4)之保存及分裝	28
3-5 反應後樣品中之EDTA螯合能力測試	29
第四章、結果與討論	32
4-1 低亞硫酸鈉(Na2S2O4)處理銅氨廢水	32
4-1-1 pH值對低亞硫酸鈉(Na2S2O4)溶液處理銅氨廢水之影響	33
4-1-2 時間及曝氣對低亞硫酸鈉(Na2S2O4)溶液處理銅氨廢水之影響	34
4-1-3 使用低亞硫酸鈉(Na2S2O4)粉末處理銅氨廢水之影響	37
4-1-4 低亞硫酸鈉(Na2S2O4)還原銅氨廢水之樣品觀察	39
4-2 低亞硫酸鈉(Na2S2O4)處理EDTA-Cu廢水	45
4-2-1 pH值對低亞硫酸鈉(Na2S2O4)溶液處理EDTA-Cu廢水之影響	45
4-2-2 時間及曝氣對低亞硫酸鈉(Na2S2O4)溶液處理EDTA-Cu廢水之影響	46
4-2-3 使用低亞硫酸鈉(Na2S2O4)粉末處理EDTA-Cu廢水之影響	48
4-2-4 低亞硫酸鈉(Na2S2O4)還原EDTA-Cu廢水之樣品觀察	50
4-3 低亞硫酸鈉(Na2S2O4)處理EDTA-Cu及銅氨廢水之比較	52
4-3-1 使用低亞硫酸鈉(Na2S2O4)粉末或溶液處理EDTA-Cu及銅氨廢水之比較	52
4-3-2 曝空氣或未曝氣對低亞硫酸鈉(Na2S2O4)處理EDTA-Cu及銅氨廢水之比較	54
第五章、結論與建議	56
5-1 結論	56
5-2 建議	57
參考文獻	58


 
圖目錄
Figure 1 不同pH下銅(Cu2+)在水中存在形式(模擬條件: 溫度25℃，銅離子濃度為2.25 E-03 M)	3
Figure 2 (a) EDTA之分子結構式(b)EDTA與重金屬螯合之分子結構式	5
Figure 3 不同pH下EDTA在水中存在的形式(模擬條件: 溫度25℃，EDTA濃度2.25 E-03M)	6
Figure 4不同pH下EDTA在水中存在的形式(模擬條件:溫度25℃；假設無固體物；Cu : EDTA = 2.25E-03 M : 2.25E-03 M)	7
Figure 5 不同形式薄膜可去除的汙染物[20]	10
Figure 6 電解法之基本構造圖	11
Figure 7 低亞硫酸鈉(Na2S2O4)之分子結構式	14
Figure 8 銅離子濃度標準曲線圖	20
Figure 9 實驗流程圖	21
Figure 10 低亞硫酸鈉溶液之靜置變化情形(a)初始顏色(b)靜置15分鐘後之顏色	23
Figure 11 曝空氣之低亞硫酸鈉溶液ORP變化	24
Figure 12 曝空氣之低亞硫酸鈉溶液外觀變化(a) 8分鐘(b) 10分鐘(b) 12分鐘	24
Figure 13 曝氮氣之低亞硫酸鈉溶液ORP變化	25
Figure 14 曝氮氣30分鐘之低亞硫酸鈉溶液外觀變化	25
Figure 15 低亞硫酸鈉接觸空氣之ORP變化	26
Figure 16 低亞硫酸鈉接觸空氣產生之外觀變化(a) 28分鐘(b) 30分鐘(b) 32分鐘	26
Figure 17 未曝氣之低亞硫酸鈉溶液ORP變化	27
Figure 18 自製分裝低亞硫酸鈉之設備	28
Figure 19 標準鈣溶液(10 mmol/L )滴定EDTA溶液之莫耳比(0.225 mmol、0.112 mmol、0.056 mmol)	31
Figure 20 銅氨在不同pH下存在形式(模擬條件:溫度25℃；假設無固體物；    Cu : NH3 = 2.25E-03 M : 9E-03 M)	32
Figure 21 不同pH下使用低亞硫酸鈉溶液處理銅氨廢水之去除率(反應條件: [Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；30 min；未曝氣)	34
Figure 22 pH9條件下使用曝氮氣(N2)、曝空氣及未曝氣方式處理銅氨廢水之去除率(反應條件: [Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；120 min)	35
Figure 23 pH9下以不同方式處理銅氨廢水之外觀 (a)曝空氣 (b)未曝氣 (c)曝氮氣	35
Figure 24 不同pH下使用曝氮氣(N2)方式處理銅氨廢水之去除率(反應條件: [Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；30 min)	36
Figure 25 不同pH下使用曝氮氣(N2)方式處理銅氨廢水之外觀 (a) pH3 (b) pH5 (c) pH7 (d) pH9 (e) pH11	37
Figure 26 不同pH下使用低亞硫酸鈉(Na2S2O4)粉末處理銅氨廢水之去除率 (反應條件: [Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；30 min；未曝氣)	38
Figure 27 [Cu]:[NH3]:[Na2S2O4]=1:4:3；pH=9.5；曝氮氣；(a)風乾；未經蒸餾水沖洗(b)風乾；經蒸餾水沖洗(c)烘乾；未經蒸餾水沖洗(d)烘乾；經蒸餾水沖洗	40
Figure 28 [Cu]:[NH3]:[Na2S2O4]=1:4:3；pH=9.5；未經蒸餾水清洗；曝氮氣；(a) (b)烘乾；SEM=50000倍及100000倍 (c) (d)風乾；SEM=50000倍及100000倍	41
Figure 29 [Cu]:[NH3]:[Na2S2O4]=1:4:3；pH=9.5；未經蒸餾水洗過；未曝氮氣；(a) (b)風乾；SEM=50000倍及100000倍(c) (d)烘乾；SEM=50000倍及100000倍	42
Figure 30 [Cu]:[NH3]:[Na2S2O4]=1:4:3；烘乾；未曝氮氣；(a) pH=9；未經蒸餾水沖洗(b) pH=9；經蒸餾水沖洗 (c) pH=9.5；未經蒸餾水沖洗(d) pH=9.5；經蒸餾水沖洗 (e) pH=10；未經蒸餾水沖洗(f) pH=10；經蒸餾水沖洗	43
Figure 31 [Cu]:[NH3]:[Na2S2O4]=1:4:3；pH=9；烘乾；未曝氮氣；(a) (b)未經蒸餾水洗過；SEM=100000倍(c) (d)經蒸餾水洗過；SEM=50000倍及100000倍	44
Figure 32 不同pH下EDTA在水中存在的形式(模擬條件:溫度25℃；假設無固體物；Cu : EDTA = 2.25E-03 M : 2.25E-03 M)	45
Figure 33 不同pH下使用低亞硫酸鈉溶液處理EDTA-Cu廢水之去除率 (反應條件: [Cu]:[EDTA]:[Na2S2O4]=1:1:3；過濾孔徑0.45 μm；30 min；未曝氣)	46
Figure 34 pH9條件下使用曝氮氣(N2)、曝空氣及未曝氣方式處理EDTA-Cu廢水之去除率(反應條件: [Cu]:[EDTA]:[Na2S2O4]=1:1:3；過濾孔徑0.45 μm；120 min)	47
Figure 35 pH9下以不同方式處理EDTA-Cu廢水之外觀(a)曝空氣 (b)未曝氣 (c)曝氮氣	48
Figure 37 [Cu]:[EDTA]:[ Na2S2O4]=1:1:3；未曝氮氣；烘乾；經蒸餾水沖洗(a) pH=5；粉末(b) pH=5；溶液(c) pH=7；粉末(d) pH=7；溶液	51
Figure 38 [Cu]:[EDTA]:[Na2S2O4]=1:1:3；未曝氮氣；烘乾；經蒸餾水沖洗(a) pH=9；粉末(b) pH=9；溶液(c) pH=11；粉末(d) pH=11；溶液	51
Figure 39 不同pH下使用低亞硫酸鈉溶液處理EDTA-Cu及銅氨廢水之去除率 (反應條件: [Cu]:[EDTA]:[Na2S2O4]=1:1:3；[Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；30 min；未曝氣)	53
Figure 40 不同pH下使用低亞硫酸鈉粉末處理含EDTA-Cu及銅氨廢水之去除率 (反應條件: [Cu]:[EDTA]:[Na2S2O4]=1:1:3；[Cu]:[NH3]:[Na2S2O4]=1:4:3；過濾孔徑0.45 μm；30 min；未曝氣)	54
Figure 41 pH9條件下使用曝氮氣(N2)、曝空氣及未曝氣方式處理EDTA-Cu及銅氨廢水之去除率(反應條件: [Cu]:[EDTA]:[Na2S2O4]=1:1:3；[Cu]:[NH3]:[Na2S2O4]=1:4:3 ;過濾孔徑0.45 μm；120 min；未曝氣)	55

 
表目錄
Table 1 典型電路板製造業原廢水污染濃度表[1, 2]	1
Table 2 EDTA-Cu之平衡常數[19]	7
Table 3 重金屬去除技術之優缺點	12
Table 4 化學還原法處理不同物質之文獻	15
Table 5 標準鈣溶液(10 mmol/L )滴定EDTA溶液	30

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