표제지
요약문
목차
1. 서론 18
1.1. 연구배경 18
1.2. 연구내용 및 범위 21
2. 이론적 배경 23
2.1. 키토산 23
2.1.1. 키토산 특성 23
2.1.2. 키토산 비드 특성 25
2.1.3. 키토산 비드에 의한 흡착 26
2.1.4. 키토산 복합 비드의 합성과 오염물질의 제거 27
2.1.5. 키토산 가교 29
2.1.6. 셀룰로오스 33
2.2. Oxyanion(산소 결합된 형태의 음이온) 처리 36
2.2.1. 비소 36
2.2.2. 6가 크롬 42
2.2.3. 인산염 44
2.2.4. 금속 이온의 처리 공법 45
2.2.5. 인산염 처리 공법 50
2.3. 등온흡착식 54
2.3.1. Langmuir 등온흡착식 54
2.3.2. Freundlich 등온흡착식 55
2.3.3. Temkin 등온흡착식 56
2.3.4. Dubinin-Radushkevich 등온흡착식 56
2.4. 반응속도모델 57
2.4.1. 유사 1차 반응속도모델 57
2.4.2. 유사 2차 반응속도모델 58
2.5. 시차주사열량계 58
2.6. 재료시험기 60
2.7. 푸리에 변환 적외선 분광분석기기 61
2.8. 주사전자현미경 62
3. 실험 방법 63
3.1. 키토산 비드 및 강도보완 비드 제조 63
3.1.1. 키토산 비드 입상화 64
3.1.2. 가교제에 의한 화학적 강도 개선 65
3.1.3. 셀룰로오스에 의한 물리적 강도 개선 66
3.2. 고강도 키토산 비드의 특성 분석 69
3.2.1. 비드의 화학적 안정성 분석 69
3.2.2. 고강도 비드 작용기 분석 70
3.2.3. 고강도 비드 표면 이미지 측정 70
3.2.4. 비드 강도 보완에 따른 물리적 강도 변화 측정 71
3.2.5. 고강도 비드의 열적 안정성 분석 71
3.3. 폐수 성상 72
3.4. 분석 방법 72
3.5. 비드 제조 조건별 오염물질 흡착 73
3.5.1. 입상화된 키토산 비드의 흡착 효율 74
3.5.2. 화학적 강도 개선에 따른 흡착 효율 비교 75
3.5.3. 건조 방식 별 비드의 제거 효율 비교 76
3.6. 고강도 비드에 의한 비소 흡착 77
3.6.1. pH에 따른 비소 흡착 77
3.6.2. As에 대한 등온흡착식 78
3.6.3. As 흡착 속도식 79
3.6.4. 공존물질 주입에 따른 As 흡착량 80
3.6.5. 흡착제 재생 후 As 흡착능 변화 82
4. 실험 결과 84
4.1. 비드 특성 분석 결과 84
4.1.1. 키토산 비드 화학적 안정성 분석 결과 84
4.1.2. 고강도 비드 작용기 분석 결과 89
4.1.3. 고강도 비드 표면 이미지 92
4.1.4. 비드 강도 보완에 따른 물리적 강도 측정 결과 96
4.1.5. 비드의 열적 안정성 변화 101
4.2. 비드 제조 조건별 오염물질 흡착 효율 변화 105
4.2.1. 입상화된 키토산의 오염물질 흡착 106
4.2.2. 화학적 강도 개선에 따른 오염물질 흡착 결과 109
4.2.3. 건조 방식에 따른 오염물질 흡착 결과 116
4.3. 비드에 의한 비소 흡착 120
4.3.1. pH에 따른 최대흡착량 120
4.3.2. As 등온흡착식 123
4.3.3. As 흡착 속도식 130
4.3.4. 공존물질에 따른 흡착량 변화 134
4.3.5. 비드 재생 후 흡착 변화 137
4.4. 키토산 비드 흡착제의 경제성 145
5. 결론 148
참고문헌 151
ABSTRACT 172
Table 2.1. Standards for wastewater discharge facilities for specific water quality hazardous substances 39
Table 2.2. Characteristics of arsenic 41
Table 2.3. Comparison of heavy metal ion removal technologies 46
Table 2.4. Various filters for water treatment and characteristics 48
Table 3.1. Experimental conditions for making GA-CB, ECH-CB 66
Table 3.2. Experiment conditions for degree of swelling 70
Table 3.3. Summary of chitosan bead characterization Analysis 71
Table 3.4. Ions to be removed and reagents 72
Table 3.5. Analysis method 73
Table 3.6. Adsorption experiment condition to find optional NaOH solution 74
Table 3.7. Adsorption experiment condition to find optional crosslink solution 75
Table 3.8. Adsorption experiment condition to find optional method of dry 76
Table 3.9. Experiment conditions for As adsorption 78
Table 3.10. Experiment conditions for isotherm equations 79
Table 3.11. Experiment conditions for isotherm equations 80
Table 3.12. Experimental conditions for adsorption efficiency according to the existence of phosphate ion 81
Table 3.13. Experimental conditions for adsorption efficiency according to the existence of TOC and NO3- in artificial ground water 81
Table 3.14. Experiment conditions for beads recycles 83
Table 4.1. Physical strength measurement results 100
Table 4.2. Glass transition temperature of beads 102
Table 4.3. isotherm constants for adsorption of HAsO₄²⁻ by GA-SCB 126
Table 4.4. isotherm constants for adsorption of HAsO₄²⁻ by GA-SCB 130
Table 4.5. Comparison of adsorption capacity of chitosan bead and activated carbon 146
Table 4.6. Comparison of the price of chitosan bead and activated carbon 147
Table 4.7. Comparison of the price per adsorption capacity 147
Fig. 1.1. Flow chart of this study 23
Fig. 2.1. Various adsorption mechanisms of chitosan beads 26
Fig. 2.2. Crosslink by glutaraldehyde 31
Fig. 2.3. Reaction of chitosan and epichlorohydrin to produce chitosan beads crosslinked by epichlorohydrin 32
Fig. 2.4. Eh-pH stability of aqueous arsenic species 37
Fig. 2.5. Synthesis od intracellular chromium metabolism and genotoxic mechanisms 42
Fig. 2.6. Distribution of hexavalent cromium type in different pH 44
Fig. 2.7. Distribution diagram for H₃PO₄ at 25℃. 45
Fig. 2.8. DSC manufactured by Perkin Elmer 59
Fig. 2.9. Micro Material Tester 60
Fig. 2.10. Fourier Transform Infra-Red Spectrometer manufactured by Thermo fisher scientific 61
Fig. 2.11. FE-SEM manufactured by HITACHI 63
Fig. 4.1. Changes in swelling of each bead by time (pH = 2) 85
Fig. 4.2. Changes in swelling of each bead by time (pH = 5) 86
Fig. 4.3. Changes in swelling of each bead by time (pH = 7) 87
Fig. 4.4. Changes in swelling of each bead by time (pH = 10) 88
Fig. 4.5. FT-IR spectra of CB, Non-S-CCB, SCB 90
Fig. 4.6. FT-IR spectra of CB, ECH-CB, GA-CB 91
Fig. 4.7. FT-IR spectra of GA-SCB 92
Fig. 4.8. SEM image of CB(a)×65, b)×500, c)×5,000, d)×50,000) 93
Fig. 4.9. SEM image of Non-S-CCB(a)×65, b)×500, c)×5,000, d)×50,000) 93
Fig. 4.10. SEM image of SCB(a)×65, b)×500, c)×5,000, d)×50,000) 94
Fig. 4.11. SEM image of GA-SCB(a)×65, b)×500, c)×5,000, d)×50,000) 95
Fig. 4.12. Physical strength measurement results ( a) CB, b) Non-S-CCB) 97
Fig. 4.12. Physical strength measurement results (c) SCB, d) ECH-CB) 98
Fig. 4.12. Physical strength measurement results (continued, e) GA-CB, f) GA-SCB) 99
Fig. 4.13. DSC result of chitosan based beads( a) CB) 102
Fig. 4.13. DSC result of chitosan based beads(b) Non-S-CCB, c) SCB) 103
Fig. 4.13. DSC result of chitosan based beads(continued, d) ECH-CB, e) GA-CB) 104
Fig. 4.13. DSC result of chitosan based beads (continued, f) GA-SCB) 105
Fig. 4.14. PO₄³⁻ removal rate of CB by NaOH concentration (C₀ = 49.154 mg/L) 107
Fig. 4.15. Cr(VI) removal rate of CB by NaOH concentration (C₀ = 50.004 mg/L) 108
Fig. 4.16. PO₄³⁻ removal rate by ECH injection(C₀ = 10.105 mg/L) 110
Fig. 4.17. PO₄³⁻ removal rate by GA injection(C₀ = 10.105 mg/L) 111
Fig. 4.18. Cr(VI) removal rate by ECH injection (C₀ = 10.317 mg/L) 113
Fig. 4.19. Cr(VI) removal rate by GA injection (C₀ = 10.317 mg/L) 114
Fig. 4.20. PO₄³⁻ removal efficiency by drying method 117
Fig. 4.21. Cr(VI) removal efficiency by drying method 119
Fig. 4.22. HAsO₄²⁻ adsorption capacity of beads by pH changes 121
Fig. 4.23. As(III) Removal rate of beads by pH changes 122
Fig. 4.24. The equilibrium isotherms for removal of HAsO₄²⁻ by GA-SCB (a) Langmuir isotherm) 124
Fig. 4.24. The equilibrium isotherms for removal of HAsO₄²⁻ by GA-SCB (b) Freundlich isotherm, c) Temkin isotherm) 125
Fig. 4.24. Physical strength measurement results(continued, d) Dubinin-Radushkevich isotherm) 126
Fig. 4.25. The equilibrium isotherms for removal of H₃AsO₃ by GA-SCB (a) Langmuir isotherm, b) Freundlich isotherm) 128
Fig. 4.25. The equilibrium isotherms for removal of H₃AsO₃ by GA-SCB(continued, c) Temkin isotherm, d)... 129
Fig. 4.26. Kinetic plots for HAsO₄²⁻ adsorption on GA-SCB bead (a) Pseudo-first-order, b) Pseudo-second-order) 132
Fig. 4.27. Kinetic plots for H₃AsO₃ adsorption on GA-SCB bead (a) Pseudo-first-order, b) Pseudo-second-order) 133
Fig. 4.28. HAsO₄²⁻ adsroption capacity of adsorption efficiency according to the existence of PO₄³⁻ 135
Fig. 4.29. HAsO₄²⁻ adsroption capacity of adsorption efficiency into artificial ground water 136
Fig. 4.30. Adsorption-desorption cycles for HAsO₄²⁻ adsorption onto CB, ECH-CB, GA-CB with H₂SO₄ 139
Fig. 4.31. Adsorption-desorption cycles for HAsO₄²⁻ adsorption onto CB, Non-S-CCB, SCB, GA-SCB with H₂SO₄ 141
Fig. 4.32. Adsorption-desorption cycles for HAsO₄²⁻ adsorption onto CB, ECH-CB, GA-CB with NaOH 143
Fig. 4.33. Adsorption-desorption cycles for HAsO₄²⁻ adsorption onto CB, Non-S-CCB, SCB, GA-SCB with NaOH 145