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제출문

요약문

SUMMARY

List of Table

List of Figure

목차

1장 서론 24

2장 국내시장 및 기술정보 31

1절 금속가공유제 종류 및 폐액 발생 현황 31

2절 금속가공 폐액에 대한 한외여과막 적용연구 34

3절 이론적 배경 38

3장 실험방법 및 장치 42

1절 오일함유폐액 및 UF 여과수에 대한 물리화학 특성분석 42

2절 분리막의 선정 및 막처리 가능성 실험 43

3절 미생물성장 억제실험 46

4절 Dynamic Membrane의 제조 50

5절 Lab. scale 최적운전 조건연구 52

6절 여과수 재이용 공정개발 54

7절 Pilot scale 적용실험 56

8절 시작품 설계, 제작 및 현장적용실험 57

9절 시작품의 외국제품과의 성능비교실험 59

4장 결과 및 고찰 60

1절 오일함유폐액 및 UF 여과수에 대한 물리화학적 특성분석 60

2절 분리막 선정 및 막처리 가능성 실험 64

1. 분리막 선정실험 64

2. 한외여과막에 의한 금속가공폐액의 막처리 가능성실험 66

가. 처리공정도 66

나. 한외여과막에 의한 금속가공폐액의 농축 67

1) 10 v／v% semi-synthetic type 절삭폐액의 농축 67

2) 3 v／v% emulsion type 절삭폐액의 농축[원문불량;p.70] 70

3) 세척폐액의 농축 73

3절 미생물 성장억제 공정에 관한 연구 75

4절 막의 개질화 연구 77

1. X-HAN을 이용한 막의 개질화 77

2. 막 재질에 따른 Dynamic 막의 효율 변화 78

3. Dynamic 막의 재현성과 안정성 80

4. Dynamic 막의 오일처리 효율 82

5. pH에 따른 X-HAN Dynamic 막의 효율 82

5절 Lab. Scale 최적 운전 조건 89

가. 최적압력 및 유속 89

나. 막세척 방법 94

6절 여과수 재이용 공정개발 97

7절 Pilot scale 적용실험 101

1. 알루미늄 가공용 세척폐액의 pilot 실험 101

2. 절삭폐액의 pilot 실험 102

8절 시작품의 현장적용실험 105

9절 시작품의 외국제품과의 성능비교실험 107

10절 시작품 현장적용에 따른 경제성 평가 109

1) 5 v／v% 세척폐액 109

2) 5 v／v% 절삭폐액 110

5장 결론 113

참고문헌 116

부록목차 118

1. 시작품의 처리공정도 상세도면 119

2. 시작품의 기초도면 120

3. Free oil separator의 상세도면 121

4. Pipe line의 상세도면 (I) 122

5. Pipe line의 상세도면 (II) 123

6. Inlet, Process, Wash tank의 상세도면 (I) 124

7. Inlet, Process, Wash tank의 상세도면 (II) 125

8. Stand-by tank의 상세도면 126

9／10. Pit tank의 상세도면 (II) 127

[title page etc.]

Presentation Statement

Abstract

Contents

Chapter 1. Introduction 24

Chapter 2. Collection of technical information and data 31

Section 1. Types of metal processing oils and status of waste water solution 31

Section 2. Survey about the concentration of metal working waste solution by using the ultrafiltration 34

Section 3. Theoretical background 38

Chapter 3. Experimental 42

Section 1. Chemical property of waste oily solution and their UF permeate 42

Section 2. Experiments for selection of suitable membrane and possibility of concentration of waste oily solution 43

Section 3. Experiments for the control of the microorganism growth 46

Section 4. Manufacture of dynamic membranes 50

Section 5. Optimum operating conditions of Lab. scale 52

Section 6. Process developments to reuse the permeate 54

Section 7. Test of pilot system 56

Section 8. Design, manufacture and test of trial products 57

Section 9. The comparative test of trial product with foreign products 59

Chapter 4. Results and Discussion 60

Section 1. Chemical property of water soluble cutting oils 60

Section 2. Experiments for selection of suitable membrane and possibility of concentration of waste oily solution 64

1. Selection of suitable membrane 64

2. Possibility test of concentration of waste oily solution 66

A. PFD of treatment system 66

B. Test of concentration of waste oily solution 67

(1) Concentration of 10 v／v% semi-synthetic type waste cutting oil 67

(2) Concentration of 3 v／v% emulsion type waste cutting oil[원문불량;p.70] 70

(3) Concentration of waste degreasing solution 73

Section 3. Studies for the process to control microorganism growth 75

Section 4. Studies for the modification of the membrane 77

1. Modification of the membrane by using X-HAN 77

2. Variations in the efficiency of the dynamic membrane according to membrane materials 78

3. Reproducibility and stability of the dynamic membrane 80

4. Efficiency of the dynamic membrane for the oil treatment 82

5. Efficiency of X-HAN dynamic membrane according to pH 82

Section 5. Optimum operating conditions of Lab. scale 89

1. Optimum pressure and flow rate 89

2. Washing method of the contaminated membrane 94

Section 6. Process developments to reuse the permeate 97

Section 7. Test of pilot system 101

1. Concentration of waste degreasing solution 101

2. Concentration of waste cutting solution 102

Section 8. Test of trial product 105

Section 9. The comparative test of trial product with foreign products 107

Section 10. Economic analysis for the use of system 109

1. 5v／v% waste degreasing solution 109

2. 5v／v% waste emulsion type cutting solution 110

Chapter 5. Concluding Remarks 113

References 116

Appendix 118

1. Detailed PFD of HCC trial system 119

2. Basic drawing of HCC trial system 120

3. Detailed drawing of free oil separator 121

4. Detailed drawing of pipe line (I) 122

5. Detailed drawing of pipe line (II) 123

6. Detailed drawing of inlet, process, wash tank (I) 124

7. Detailed drawing of inlet, process, wash tank (II) 125

8. Detailed drawing of stand-by tank 126

9. Detailed drawing of pit tank 127

Table 1. R & D. yearly goals and contents. 26

Table 2. The amount of water soluble waste metal working fluids generated in korea, 1994 33

Table 3. Specification of ultrafiltration membrane used. 45

Table 4. Case study for reasons of metal processing oil exchange. 46

Table 5. Case study for the duration of metal processing oil use. 47

Table 6. Membrane Characteristics 51

Table 7. Chemical properties of waste degreaser, cutting oil and their UF permeates 60

Table 8. The number of colonies in samples by colony check. 75

Table 9. Permeate quality of treated oil by dynamic membrane. 82

Table 10. Water flux variations according to operating pressure. 91

Table 11. Washing test of OHP films coating with fouling materials in beaker 96

Table 12. The mean diamete of emulsion of 5 v／v % EC-50 cutting oil diluted in U／F permeates treated by ozone. 100

Table 13. Refractive index of 5 v／v % EC-50 cutting solutions diluted in U／F permeates treated by ozone. 100

Table 14. Economic analysis for the treatment of 5 v／v% waste degreaser using the HCC trial system. 109

Table 15. Cost saving by using the HCC trial system. 110

Table 16. Cost evaluation for the treatment of 5 v／v% waste cutting oil using the HCC trial system. 111

Table 17. Economics by using the HCC trial system. 112

Figure 1. Modes of an ultrafiltration membrane system operation. 36

Figure 2. Process Flow Diagram (PFD) for the treatment of waste cutting oils by using an ultrafiltration membrane. 43

Figure 3. Schematic of experimental set-up for the bio-oxidation. 48

Figure 4. Schematic diagram of experimental device. 50

Figure 5. Process flow diagram of Lab. System #1. 52

Figure 6. Process flow diagram of Lab. System #2. 53

Figure 7. Process flow diagram of the pilot scale U／F system. 57

Figure 8. PFD of the trial HCC UF products 58

Figure 9. Variations in emulsion size distributions of 10 v／v% semi-synthetic type cutting oil according to diluents. 62

Figure 10. Emulsion size distributions of 10 v／v% semi-synthetic type cutting oil and its waste. 65

Figure 11. Performance tests of membranes for concentration of 10 v／v% semi-synthetic type cutting oils. 67

Figure 12. Temperature and flux variations according to volume reduction for 10 v／v% semi-synthetic type waste cutting oil when HYDE Mini UF system used. 69

Figure 13. Flux variations of 3 v／v% emulsion type new and waste cutting oils. 70

Figure 14. Flux differences between a new and an used UF module when only the permeate was used for the cleaning step.[원문불량;p.70] 72

Figure 15. CODs of UF membrane (30,000 dalton) permeates according to the volume reduction of the new (CODCr ＝ 76,800 ppm, CODMn ＝ 42,300 ppm) and the waste (CODCr ＝ 90,000 ppm, CODMn ＝ 49,610 ppm) of 3 v／v % emulsion type cutting oils.(이미지참조) 73

Figure 16. Temperature and flux variations according to Volume Reduction for 5 v／v% waste washing solution when HYDE Mini UF system used. 74

Figure 17. Flux variation with concentration factor during the oil treatment by dynamic hollow fiber membrane. 77

Figure 18. Comparison of oil treatment efficiency with different membrane materials. 79

Figure 19. Reproducibility of recoated dynamic membrane in oil treatment 81

Figure 20. Titiration curve for X-HAN with 1N NaOH solution. 83

Figure 21. Dynamic membrane efficiency precoated with X-HAN at various pH. 85

Figure 22. Particle size distribution of X-HAN at different pH. 86

Figure 23. Analysis of dynamic membrane filtration with cake filtration model. 87

Figure 24. Flux variations of 5v／v% EC-50 cutting oil according to feed pressure and tube-side NRe(이미지참조) of Lab system #1. 90

Figure 25. Effects of feed pressure on the flux of waste degreaser through used U／F membrane (30,000 dalton). 92

Figure 26. Effects of tube-side velocity (NRe)(이미지참조) on the flux of waste degreaser through used U／F membrane (30,000 dalton). 93

Figure 27. UF flux variations of waste degreaser including floating oil. 94

Figure 28. UF flux variations of waste degreaser when floating oil is removed partially. 95

Figure 29. Flux recovery by chemical washing in contaminated UF membrane 97

Figure 30. Ozonation effects on CODCr(이미지참조) of permeate and foaming rate of 5 v／v % EC-50 cutting oils diluted in U／F permeates treated by ozone. 99

Figure 31. Flux variations of waste degreaser(5% Cerfa Kleen 5380B) in pilot scale experiments. 102

Figure 32. Flux variations of waste cutting oil(5% EC-50) in pilot scale experiment. 104

Figure 33. Flux variations of waste cutting oil(Houghto 60G) in pilot scale experiment. 104

Figure 34. Flux variations of waste degreaser(5% Cerfa Kleen 5380B) in the HCC trial UF product. 105

Figure 35. Flux variations of waste degreaser(5% Cerfa Kleen 5380D) in the HCC trial UF product. 106

Figure 36. Flux variations of waste cutting oil(Houghto 60G) in the HCC trial UF product. 107

Figure 37. Flux variations of waste degreaser(5% Cerfa Kleen 5380D) of in the HCC trial UF product and Hyde OF system. 108