本研究探討疏水膜與疏水氫氧化銅塗層網過濾結合氣泡萃取去除含銅廢水。實驗中用到兩種薄膜過濾方式和一套疏水氫氧化銅塗層網系統。對於薄膜系統，首先探討pH以及D2EHPA劑量對去除銅和化學需氧量的影響，隨後探討氣泡萃取系統釋放壓力對去除銅和化學需氧量的影響，最後探討D2EHPA與煤油比例對去除銅和化學需氧量的影響。結果顯示，濃度為每升5毫摩爾的銅溶液在pH值為5以及D2EHPA劑量為1.61克和釋放壓力為0.3 MPa，D2EHPA/煤油的比例為1: 10的條件下，利用薄膜過濾系統後，銅的去除效率能達到98%，但是化學需氧量的去除效率只有60%，且薄膜堵塞的情況嚴重。
對於疏水氫氧化銅塗層網系統，首先探討水力停留時間對去除化學需氧量的影響，隨後探討萃取劑/水的比例對去除化學需氧量的影響，最後討論D2EHPA/煤油比例對去除銅和化學需氧量的影響。結果顯示，濃度為每升5毫摩爾的銅溶液，在pH值為5以及D2EHPA劑量為1.61克和釋放壓力為0.3 MPa，D2EHPA/煤油的比例為1: 10，水力停留時間為1分鐘的條件下，利用疏水氫氧化銅塗層網系統過濾後，銅的去除效率能達到98%。並且COD的去除效率優於薄膜系統，可以保持在80%-85%，且沒有堵塞的情況產生。

Integration of hydrophobic membrane or superhydrophobic copper hydroxide coated mesh filtration with a compressed air-assisted solvent extraction system was employed for copper removal. Two sets of membrane systems, namely, cross-flow system and dead-end system, and one set of hydrophobic copper hydroxide coated mesh system were used in the experiment. For the membrane system, the effects of pH and D2EHPA dosage on copper removal and COD removal were discussed first. Then the effects of the compression pressure of the compressed air-assisted solvent extraction system on copper removal and COD removal were discussed. The effects of different ratios of D2EHPA and kerosene on copper removal and COD removal were discussed at the end. The copper concentration in the wastewater used in the experiment is 5 mM. The best experimental condition is pH 5, D2EHPA dosage of 1.61 g, compression pressure of 0.3 MPa, and D2EHPA/kerosene ratio of 1:10. With the integration of the membrane system, the removal rate of copper can reach 98%, but the removal rate of COD is only 60%, and membrane fouling is serious.
For the hydrophobic copper hydroxide coated mesh system, the effects of hydraulic retention time on COD removal were discussed first. Then the effects of different extractant/water ratios on COD removal were discussed. The effects of different D2EHPA/kerosene ratios on copper removal and COD removal were discussed at the end.
The results showed that for the copper solution with a concentration of 5 mM under the conditions of pH 5, a D2EHPA dose of 1.61 g, a compression pressure of 0.3 MPa, a D2EHPA/kerosene ratio of 1:10, and a hydraulic retention time of 1 minute, the copper removal efficiency can reach 98% with the integration of the superhydrophobic copper hydroxide coated mesh system. The removal of copper in membrane system and superhydrophobic copper hydroxide coated mesh system are almost the same, but the superhydrophobic copper hydroxide coated mesh system has a better COD removal, The COD removal rate maintained at 80%-85% for a long operation time of 12 hrs, and there is no clogging.

CONTENTS
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
中文摘要 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Literature reviews . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1 Metal extraction with D2EHPA . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Compressed air-assisted solvent extraction for metal removal . . . . . . 6
2.3 Membrane for solvent/water separation . . . . . . . . . . . . . . . . . . 8
2.4 hydrophilic and hydrophobic materials for solvent/water separation . . 11
2.5 Membrane Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1 Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.1 CASX system . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.2 Cross-
ow and dead-end membrane system . . . . . . . . . . . . 19
3.2.3 Superhydrophobic copper hydroxide coated mesh . . . . . . . . 21
3.3 Experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.3.1 Membrane system . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3.2 SCM system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.4 Analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1 Selection of the optional conditions for CASX . . . . . . . . . . . . . . 28
4.2 Membrane system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.2.1 Effects of CASX compression pressure on Cu removal . . . . . . 34
4.2.2 Effects of carrier/kerosene ratio . . . . . . . . . . . . . . . . . . 37
4.3 SCM system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.3.1 Effects of HRT on the oil/water separation . . . . . . . . . . . . 43
4.3.2 Effects of extractant/water ratio . . . . . . . . . . . . . . . . . . 46
4.3.3 Effects of carrier/diluent ratio . . . . . . . . . . . . . . . . . . . 47
4.3.4 Optimization of experimental conditions for efficient Cu removal 49
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

LIST OF TABLES
2.1 Degreasing separation materials with hydrophobic and hydrophilic properties manufactured by different methods . . . . . . . . . . . . . . . . . 14

LIST OF FIGURES
2.1 Chemical structure of D2EHPA . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Distribution of extractant in organic and aqueous phase [24]. . . . . . . 5
2.3 Micro-sized solvent-coated air bubbles (MSAB) for metal extraction generated under various pressure (left:100 kPa, middle:200 kPa, and right:300 kPa). (a) right after samples prepared, (b) 30 min, and (c) 5h after solvent prepared [4]. . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4 Schematic representing basic principles involved in membrane separation[29]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5 Schematic of the cross-flow experimental setup [31]. . . . . . . . . . . . 10
2.6 A simple demonstration of oil/water separation for a hydrophilic mesh[34]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.7 The prepared coating mesh fi lm shows special wettability, with both super-hydrophobic and super-oleophilic characteristics [18]. . . . . . . . 13
2.8 A model device for the separation of hydrophobic solvents and water,
a mixture of solvents and water is added at a rate of one droplet persecond [35]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.9 Membrane fouling mechanisms [6]. . . . . . . . . . . . . . . . . . . . . . 16
3.1 Schematic diagram of the compressed air-assisted solvent-coated extraction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2 Schematic diagram of the cross flow membrane  filtration system . . . . . 20
3.3 Schematic diagram of the dead-end  filtration system . . . . . . . . . . . 21
3.4 Schematic diagram of SCM system . . . . . . . . . . . . . . . . . . . . 23
4.1 The relationship between different pH values and D2EHPA dosage on
COD removal rate (0.45 μm fi lter). Experimental conditions: Compression pressure of 0.3 MPa and the ratio of D2EHPA/kerosene of 1:10. . . 29
4.2 The relationship between different pH values and D2EHPA dosage on COD removal rate (0.22 μm fi lter). Experimental conditions: Compression pressure of 0.3 MPa and the ratio of D2EHPA/kerosene of 1:10. . . 30
4.3 0.45 and 0.22 μm  filter results for the D2EHPA/Cu (II) molar ratio of 4. 31
4.4 The relationship between different pH values and D2EHPA dosage on Cu removal rate (0.45 μm  lter). Experimental conditions: Compression pressure of 0.3 MPa and the ratio of D2EHPA/kerosene of 1:10. . . . . 32
4.5 The relationship between different pH values and D2EHPA dosage on Cu removal rate (0.22 μm  lter). Experimental conditions: Compression pressure of 0.3 MPa and the ratio of D2EHPA/kerosene of 1:10. . . . . 33
4.6 Membrane flux as a function of released pressure. Experimental conditions: D2EHPA dosage of 1.61 g, the ratio of D2EHPA:Kerosene of 1:10 and pH of 5 (cross-flow system). . . . . . . . . . . . . . . . . . . . . . . 35
4.7 The relationship between time and pressure (cross-flow system). . . . . 36
4.8 Cu removal as a function of released pressure. Experimental conditions: D2EHPA dosage of 1.61 g, the ratio of D2EHPA:kerosene of 1:10 and pH is 5 (cross-flow system). . . . . . . . . . . . . . . . . . . . . . . . . 37
4.9 COD removal as a function of released pressure. Experimental conditions: D2EHPA dosage of 1.61 g, the ratio of D2EHPA:Kerosene of 1:10 and pH of 5 (cross-flow system). . . . . . . . . . . . . . . . . . . . . . . 38
4.10 Membrane flux as a function of D2EHPA/kerosene ratio. Experimental
conditions: D2EHPA dosage of 1.61 g, the compression pressure of 0.3 MPa, pH of 5 and the TMP of the membrane system of 0.1 MPa. . . . 39
4.11 Membrane resistance as a function of D2EHPA/kerosene ratio. Experimental conditions:D2EHPA dosage of 1.61 g, the compression pressure of 0.3 MPa, pH of 5 and the TMP of the membrane system of 0.1 MPa. 40
4.12 Cu removal as a function of D2EHPA/kerosene ratio. Experimental conditions: D2EHPA dosage of 1.61 g, the compression pressure of 0.3 MPa, pH of 5 and the TMP of the membrane system of 0.1 MPa. . . . 41
4.13 COD removal as a function of D2EHPA/kerosene ratio. Experimental conditions: D2EHPA dosage of 1.61 g, the compression pressure of 0.3 MPa, pH of 5 and the TMP of the membrane system of 0.1 MPa. . . . 42
4.14 COD removal e ciency as a function of time by gravity separation . . . 43
4.15 Extended test of SCM for di erent HRT. Experimental conditions: The ratio of kerosene/DI water of 1:100. . . . . . . . . . . . . . . . . . . . . 44
4.16 Extended test of SCM for the separation of extractant/water. Experimental conditions: HRT of 1 min, the ratio of D2EHPA/kerosene of 1:10 and the ratio of extractant/DI water of 1:100. . . . . . . . . . . . . 45
4.17 Pressure profile v.s. number of bed volume for a long-term SCM test.
Experimental conditions: HRT of 1 min, the ratio of D2EHPA/kerosene of 1:10 and the ratio of extractant/DI water of 1:100. . . . . . . . . . . 46
4.18 COD removal as a function of extractant/water ratio. Experimental conditions: HRT of 1 min, the ratio of D2EHPA: kerosene of 1:10 and the compression pressure of 0.3 MPa. . . . . . . . . . . . . . . . . . . . 47
4.19 COD removal as a function of carrier/kerosene ratio. Experimental conditions: HRT of 1 min, compression pressure of 0.3 MPa and the extractant/water ratio of 1:150. . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.20 Test of SCM for removal copper. Experimental conditions: pH of 5, HRT of 1 min, D2EHPA dosage of 1.61 g, the ratio of D2EHPA: kerosene of 1:10 and compression pressure of 0.3 MPa. . . . . . . . . . . . . . . . . 50

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