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제출문
요약문
SUMMARY
List of Figure
List of Table
목차
제1장 서론 19
제2장 이론적 고찰 21
1절 불소와 중금속 함유 폐수의 처리및 재이용 21
1. 폐수 발생 공정 및 폐수 처리 사례 21
2. 소석회(Lime)를 이용한 중화 및 화학침전 처리 25
3. 나노여과(Nanofiltration) 28
2절 RO/NF 시스템의 전처리 연구 33
1. RO/NF 시스템의 전처리의 종류및 특성 33
2. 무기염이 함유된 폐수의 전처리 연구현황 39
3절 나노여과의 이온배제 43
1. 나노여과에서의 이온 배제 메카니즘 43
2. 나노여과의 이온 배제율에 영향을 미치는 인자. 53
4절 나노여과의 막오염 현상에 관한 이론 64
5절 결정에 의한 막오염에 영향을 주는 인자. 72
1. 결정화 메카니즘 72
2. 유속의 영향 78
3. 작동압력의 영향 79
6절 나노여과를 이용한 공장규모의 설비 개발 81
1. 사례연구 81
2. 공장규모 장치의 설계 86
3. 분리막 설비의 성능 예측을 위한 모델 90
7절 무기염에 의한 막오염의 조절 및 세척 92
1. 스케일 형성 특성 92
2. 스케일 형성의 예측 96
3. 스케일 물질의 제거 및 막오염의 세척 97
3장 실험 101
1절 실험장치 101
2절 분석방법 104
1. 이온 분석 104
2. 규소와 납의 농도분석 105
3. 입자 크기 분석 105
3절 실험내용 106
1. 재이용 방해성분 규명 및 기존 공정의 개선 106
2. 나노여과를 이용하여 재활용수를 여과할때의 막오염 현상 연구 107
3. Full Plant의 설계 및 작동 110
4장 실험 결과 및 고찰 112
1절 재이용 방해성분 규명 및 기존 공정의 개선 112
1. 폐수의 재활용을 방해(방헤)하는 성분 규명 112
2. 소석회를 이용한 중화 및 화학침전 처리 114
3. 전기 투석(Electrodialysis reversal,EDR)을 이용한 연구 118
4. 기존 폐수처리 공정의 재검토 (나노여과의 전처리)[원문불량;p.105] 121
2절 나노여과를 이용한 처리수 재이용 시스템 개발 124
1. 나노여과(Nanofiltration,NF)의 도입 124
2. 나노여과의 이온배제 특성 130
3. 나노여과의 막오염 현상 연구 138
3절 Full Plant의 설계 및 작동 162
1. 연속식 장치를 이용한 실험 162
2. Full Plant의 설계 166
3. 처리수 재이용 시스템의 운전 172
4. 공정의 이상유무 검토 199
5. 경제성 평가 200
5장/4장 결론 202
6장/5장 참고문헌 205
[title page etc.]
Contents
I. Introduction 19
II. Background 21
1. Treatment and Reuse of Wastewater Containing Lead and Fluoride 21
(1) Waste generation process 21
(2) Lime treatment 25
(3) Nanofiltration(NF) 28
2. Pretreatment for RO/NF 33
(1) Characteristics of pretreatment process 33
(2) State of art in pretreatments(prtreatments) for RO/NF 39
3. Ion Rejection Characteristics in NF 43
(1) Mechanisms for ion rejection in NF 43
(2) Factors that affect the ion rejection 53
4. Theories for NF Fouling Phenomena 64
5. Factors that Affect the Fouling due to Crystal Formation 72
(1) Crystallization mechanisms 72
(2) Effect of flow velocity 78
(3) Effect of operation pressure 79
6. Development of Full-Scale NF Plant 81
(1) Case studies 81
(2) Design factors 86
(3) Models for predicting plants performance 90
7. Scale Control and Cleaning 92
(1) Scale formation phenomena 92
(2) Prediction of scale formation 96
(3) Membrane Cleaning 97
III. Experiments 101
1. Experimental Equipments 101
2. Analytical Methods 104
3. Experimental Methods 106
IV. Results and Discussion 112
1. Preliminary Studies 112
(1) Components that hinder recycling of wastewater 112
(2) Lime treatment 114
(3) EDR 118
(4) Evaluation of existing process[원문불량;p.105] 121
2. Development of NF Process for Wastewater Recycling 124
(1) Introduction of NF 124
(2) Ion rejection 130
(3) Fouling of NF 138
3. Design and Operation of Full Plant 162
(1) Experiments in Continuous system 162
(2) Design 166
(3) Operation 172
(4) Review of existing process 199
(5) Economical Analysis 200
V/IV. Conclusion 202
VI/V. References 205
Table 1. The Water Discharge Limits of Various Regions in Korea 23
Table 2. Technical Data of NF Membranes 102
Table.3. Conditions of Ion Chromatography Analysis 104
Table.4. Conditions of Atomic Absorption Spectrophotometry 105
Table 5. Composition Analysis (White scum & Scrubber scale) 112
Table 6. Quality of Treated Wastewater & Water Quality Criteria 113
Table 7. Efficiency of Lime Treatment 117
Table 8. Operating condition of EDR 120
Table 9. Efficiency of EDR 120
Table 10. Composition of Wastewater after Pretreatment with 0.45㎛ MF 122
Table 11. Composition of Membrane Fouling Material 126
Table 12. Composition of NF Permeate & Retentate 130
Table 13. Composition of NF Feed 137
Table 14. Change of Permeate Composition with pH 137
Table 15. Change of Ion Rejection Efficiencies with pH 137
Table 16. The Composition of Feed and Permeate of NF-45 139
Table 17. The Composition of Feed and Permeate of NF-40 141
Table 18. The Composition of Feed and Permeate of MPT-34A 143
Table 19. Estimation of Scale Formation Quantity during Nanofiltration 144
Table 20. Flow velocity Effect on the Composition of Feed and Permeate of MPT-34A 156
Table 21. Parameters for calculating(caculating) minimum membrane areas to get constant flow rate. 169
Table 22. Operating Conditions of Full Plant 170
Table 23. Composition of Retentate and Permeate in Full Plant NF equipment. 175
Table 24. Operating History of Full Plant Equipment 176
Table 25. Solubilities of Scales in Various Cleaning Reagent 180
Table 26. Composition of Scales formed in Microfilters during Continuous Runs. MF 1: 1 ㎛ microilter, MF 2 : 0.45 ㎛ microfilter 188
Table 27. Changes of Compositions of Wastewater according to Time. 199
Table 28. Economic Analysis for Cleaner Production (unit: Thousand won) 201
Fig.1. Schematic potential energy profile in ionic transport in membrane. 49
Fig.2. Schematic representation of preferential sorption-capillary flow mechanism for reverse osmosis separations of sodium chloride from aqueous solutions. 51
Fig.3. Zeta potentials of the nanofiltration membranes at different pH. Salt solution used=1.0mM KCI, T=25 ℃ [48]. 56
Fig.4. Change of pH in RO process. Feed : NaCl solution [50, 51]. 59
Fig.5. Relationships between rejection and flux [53]. 61
Fig.6. Mass transport considerations for ions and particles[65]. (a) Midchannel concentration profiles of NaCl and CaSO₄at steady state. (b) Particle diffusivity as a function of particle radius. 70
Fig.7. Resistances due to crystal formation in NF membranes. 75
Fig.8. Flux vs. mass according to the crystallization mechanism 76
Fig.9. Procedures to calculate each resistance term [72]. 77
Fig.10. Factors affecting on membrane flux. (a) Variation of polarization modulus according to flow velocity (b) Membrane flux and rejection vs. applied pressure [22]. 80
Fig.11. Schematic diagram of a two-stage feed and bleed plant [81]. 87
Fig.12. Operation types in NF/RO plant 88
Fig.13. Effect of crystal size on dissolution rate. 99
Fig.14. Schematic diagrams of nanofiltration unit. (a) plate and frame (b) spiral wound & tubular 103
Fig 15. Residual Concentration vs. Lime dose(g/L) 114
Fig.16. (Si Conc. & Sludge Production) vs. Lime dose 115
Fig.17. Solubility equilibria for amorphous silica(s). 116
Fig.18. Flow diagram of EDR 119
Fig.19. Particle size distributions of treated wastewater....[원문불량;p.105] 123
Fig.20. Flux vs Operating time (Total Recycle Mode) 125
Fig.21. Flux & turbidity variation according to the concentration factor : NF retentate was directly recycled to the feed tank. 125
Fig.22. Scanning electron micrograph of membrane foulants. 127
Fig.23. ESCA of membrane fouling material 128
Fig.24. Effect of membrane cleaning. 129
Fig.25. Sulfate ion concentration vs.concentration factor. 132
Fig.26. pH vs. Concentration Factor : pH of initial feed=9.0 133
Fig.27. pH vs. Concentration Factor : pH of initial feed=5.52 134
Fig.28. Flux vs. concentration factor at the flow rate of 0.6 m/sec. Membrane : plate and frame module with NF-45 (a) Flux and conductivity variation (b) Flux and average particle size. 139
Fig.29. Flux vs. concentration factor at the flow rate of 0.6 m/sec. Membrane : spiral wound module with NF-40 142
Fig.30. Flux vs. concentration factor at the flow rate of 0.6 m/sec. Membrane : tubular module with MPT-34A 143
Fig.31. Flux vs.time in case of total recycle Membrane : plate and frame module with NF-45 146
Fig.32. Flux vs.time in case of total recycle Membrane : spiral wound module with NF-40 148
Fig.33. Fluid flow in spacer-filled channels 149
Fig.34. Flux vs.time in case of total recycle Membrane : tubular module with MPT-34A 151
Fig.35. Effect of prefiltration on NF flux. Membrane : plate and frame NF-45, flow rate : 0.6 m/sec 153
Fig.36. Effect of prefiltration on NF flux. Membrane : plate and frame NF-45, flow rate : 1.6 m/sec 154
Fig.37. Effect of prefiltration on NF flux. Membrane : spiral wound NF-40, flow rate : 0.6 m/sec 157
Fig.38. Particle size distributions of NF retentate of MF-NF hybrid system (CF=2.5) 157
Fig.39. Flux vs.time in case of total recycle with 0.45 ㎛ MF Membrane : spiral wound with NF-40(○:Flux, ●:Conductivity, ▲:Turbidity) 158
Fig.40. Effect of prefiltration on NF flux. Membrane : tubular MPT-34A, flow rate : 0.6 m/sec 159
Fig.41. Depressurization effect on MF-NF hybrid system. (a) Flux enhancement by depressurization. (b) Flux and conductivity vs. time during depressurization. 160
Fig.42. Continuous test equipment of MF-NF hybrid system. 163
Fig.43. Flux vs time in the case of continuous operation at CF=2. 164
Fig.44. Flux vs time in the case of continuous operation at CF=5 165
Fig.45. Comparison of flux between NF and MF MF-NF hybrid system. 166
Fig.46. Flux and conductivity variation according to the concentration factor. Membrane : SU-610, four inch spiral wound module. 167
Fig.47. Comparison of concentration reduction(F) between experimental data and linear relationship. ● : experimental data, ― : theoretical Membrane : SU-610, four inch spiral wound module. 168
Fig.48. Total required membrane area as a function of concentration factor at first stage for a two-stage membrane cascade 169
Fig.49. Schematic diagram of full plant equipment. 171
Fig.50. Flux and conductivity variation according to time in the first stage. ● : Flux, □ : Conductivity 173
Fig.51. Flux and conductivity variation according to time in the fast stage. ● : Flux, □ : Conductivity 174
Fig.52. Changes of flux according to operating time at the first stage. 177
Fig.53. Changes of flux according to operating time at the second stage. 178
Fig.54. Changes of permeability according to operating time. (● : First stage, ■ : Second stage) 179
Fig.55. Changes of inlet and outlet pressure of NF membranes according to operating time in the first stage (● : inlet pressure, ■ : outlet Pressure) 181
Fig.56. Changes of inlet and outlet pressure of NF membranes according to operating time in the second stage (● : inlet pressure, ■ : outlet pressure) 182
Fig.57. Comparison of pressure drops in NF at first and second stages (● : first stage, ■ : second stage) 183
Fig.58. Changes of pressure drop in MF according to operating time at the first stage (● : 1㎛ MF, ■ : 0.45㎛ MF) 184
Fig.59. Scale formation in the microfilter (first stage 1 ㎛ MF). 184
Fig.60. Schematic diagram of "backflushing to MF" operation. 185
Fig.61. Changes of pressure drop in MF according to operating time at the first stage (● : 1㎛ pm MF, ■ : 0.45㎛ MF) 186
Fig.62. Comparison of pressure drops in MF at first and second stages (● : first stage, ■ : second stage) 187
Fig.63. Pressure drop in prefilter. 188
Fig.64. Changes of total treatment capacity according to the time. 190
Fig.65. Feed and permeate conductivity changes according to time at first stage. (● : Feed, ■ : Permeate) 191
Fig.66. Retentate and permeate conductivity changes according to time at second stage (● : Retentate, ■ : Permeate) 191
Fig.67. Concentration of Ca and SO₄in the Feed of first stage.(● : Ca, ■ : SO₄) 193
Fig.68. Concentration of Ca and SO₄in the permeate of first stage(● : Ca, ■ : SO₄) 193
Fig.69. Concentration of Ca and SO₄in the retentate of second stage.(● : Ca, ■ : SO₄) 194
Fig.70. Concentration of Ca and SO₄in the permeate of second stage.(● : Ca, ■ : SO₄) 195
Fig.71. Concentration of monovalent ions and SiO₂in the permeate of second stage.(● : K, ■ : Na, ▲ : Cl, ▼ : F, ◆ : SiO₂) 196
Fig.72. Ion rejections of K and Na ions according to time. (● : K, ■ : Na) 197
Fig.73. Ion rejections of Cl, F and SiO₂according to time.(● : Cl, ■ : F, ▲ : SiO₂) 197
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