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제1장. 서론 14

제1절. 연구개발의 중요성 및 필요성 16

제2절. 연구개발의 국내·외 현황 18

1. 국내 연구 현황 18

2. 국외 연구 현황 18

제3절. 연구개발대상 기술의 차별성 25

제2장. 연구개발의 목표 및 내용 28

제1절. 연구의 최종 목표 30

제2절. 연도별 연구개발의 목표 및 평가방법 31

제3절. 연도별 추진체계 32

제3장. 연구개발 결과 및 활용계획 34

제1절. 연구개발 결과 및 토의 36

1. 1차년도 연구개발 수행 내용 36

(1) 바이오 수소 가스 생산 증대를 위한 기초 연구 36

A. 운전온도와 Inhibitor 주입에 의한 혐기성 메탄 생성 미생물의 활성 억제 36

B. 수소 분압 조절에 의한 혐기성 메탄 생성 미생물의 활성 억제 및 수소 생산 미생물의 활성 증대 46

(2) 막분리-조합형 수소 배출 시스템이 결합된 연속 운전식 바이오 수소 생산 반응조 구축 53

A. 반응조 내 수소 배출을 위한 gas purging 용 분리막 선정 53

B. 수소 생성 미생물의 고농도 유지를 위한 외부 분리막 설치 및 운전 54

C. 막분리-조합형 수소 배출 시스템이 결합된 바이오 수소 생산 반응조 설치 및 운전 58

2. 2차년도 연구개발 수행 내용 62

(1) 바이오 수소 가스 생산 증대를 위한 핵심 연구 62

A. 열처리에 의한 혐기성 메탄 생성 미생물의 활성 억제 및 수소 생성 미생물의 활성 증대 62

B. pH조절을 통한 혐기성 메탄 생성 미생물의 활성 억제 및 수소 생성 미생물의 활성 증대 67

(2) 막분리-조합형 연속 운전식 바이오 수소 생산 반응조 운전 결과 86

A. 효율적인 반응조 내 수소 분압 조절 시스템 구성 86

B. 다양한 운전 조건에서의 막분리-조합형 바이오 수소 생산 반응조의 연속 운전 결과 87

C. 분자생물학적 분석기법 이용 연속 운전식 반응조 내 미생물 군집 분석 100

D. 효율적인 고순도 수소 분리 시스템 구성 및 운전 110

E. 바이오 수소가스 생산 공정의 경제성 분석 113

제2절. 연구개발 결과 요약 114

제3절. 연도별 연구개발목표의 달성도 116

1. 1차년도 연구개발목표의 달성도 116

2. 2차년도 연구개발목표의 달성도 116

제4절. 연도별 연구성과 117

1. 1차년도 연구성과 117

2. 2차년도 연구성과 117

제5절. 관련분야의 기술발전 기여도 119

1. 기술적·환경적 측면 119

2. 경제적·산업적 측면 119

제6절. 연구개발 결과의 활용계획 121

제4장 참고문헌 122

표목차

Table 1-1. Various bio-hydrogen production processes (Kumar and Das, 2001) 20

Table 1-2. Various anaerobic bio-hydrogen gas production processes 24

Table 3-1. Characterization results of digester sludge 64

Table 3-2. Effect of initial pH adjustment on the bio-hydrogen gas production from municipal digested sludge 83

Table 3-3. Comparison of bio-hydrogen maximum yields obtained from the present study with previously reported values in the literature 84

Table 3-4. Processed COD values obtained from the batch bio-hydrogen gas production processes under various operational conditions 85

Table 3-5. Effect of various operational parameters on the bio-hydrogen gas production from municipal digested sludge 97

Table 3-6. Processed COD values obtained from the semi-continuous flow bio-hydrogen gas production processes under various operational conditions 99

Table 3-7. Optimization of PCR 101

Table 3-8. Optimization of RFLP 104

Table 3-9. T-RFLP analysis results of microorganisms in bioreactor 106

Table 3-10. Oligonucleotide probe used in this study 107

Table 3-11. Separation of hydrogen gas produced from the membrane-coupled continuous-flow bio-hydrogen gas production process 112

그림목차

Figure 1-1. Fermentative hydrogen gas production from renewable resources 21

Figure 1-2. Metabolic pathway of fermentative hydrogen gas production (조지혜, 2006) 22

Figure 3-1. Cumulative total gas production in the methanogenic cultures amended with different initial BESA at 20℃ (A) and 35℃ (B). 39

Figure 3-2. Cumulative methane gas production in the methanogenic cultures amended with different initial BESA at 20℃ (A) and 35℃ (B). 40

Figure 3-3. VFAs profile in the methanogenic cultures amended with different initial BESA at 20℃ (A) and 35℃ (B). 43

Figure 3-4. VFAs concentration profile in the methanogenic cultures amended with 10 (A and C) and 25 g/L BESA (B and D) at 20℃ (A and B) and 35℃ (C and D). 44

Figure 3-5. Fermentative bio-hydrogen gas production from organic wastes 45

Figure 3-6. Fermentative bio-gas production under various hydrogen partial pressure 47

Figure 3-7. Cumulative total gas production under various gas purging conditions in batch cultures amended without (A) and with BESA (B) at 35℃. 49

Figure 3-8. Cumulative methane gas production under various gas purging conditions in batch cultures amended without (A) and with BESA (B) at 35℃. 50

Figure 3-9. Cumulative hydrogen gas production under various gas purging conditions in batch cultures amended without (A) and with BESA (B) at 35℃. 52

Figure 3-10. Hollow fiber membrane for gas purging 53

Figure 3-11. 10-L glass reactor equipped with gas purging membrane 54

Figure 3-12. Crossflow external membrane module (A) and fouled PVDF membrane (B) 55

Figure 3-13. Permeate flux as a function of the TMP for MF (A) and UF membrane (B) 56

Figure 3-14. Developed flat-sheet type membrane module 57

Figure 3-15. Flow pattern of developed membrane module by using CFD modeling technique 57

Figure 3-16. Bio-hydrogen gas production process with membrane-enhanced hydrogen discharge system 58

Figure 3-17. Organic removal profiles in a continuous-flow bioreactor 59

Figure 3-18. Processed COD profiles in a continuous-flow bioreactor 60

Figure 3-19. Cumulative hydrogen, methane, and VFAs profiles in batch cultures amended with heat-treated digester sludge 64

Figure 3-20. VFAs profiles in batch cultures amended with heat-treated digester sludge 66

Figure 3-21. Profiles of processed COD in batch cultures amended with heat-treated digester sludge 66

Figure 3-22. Cumulative hydrogen, methane, and VFAs profiles in batch cultures at initial pH 5 without an amendment of BESA 69

Figure 3-23. VFAs profiles in batch cultures at initial pH 5 without an amendment of BESA 69

Figure 3-24. Profiles of processed COD in batch cultures at initial pH 5 without an amendment of BESA 70

Figure 3-25. Cumulative hydrogen, methane, and VFAs profiles in batch cultures at initial pH 9 without an amendment of BESA 71

Figure 3-26. VFAs profiles in batch cultures at initial pH 9 without an amendment of BESA 72

Figure 3-27. Profiles of processed COD in batch cultures at initial pH 9 without an amendment of BESA 72

Figure 3-28. Cumulative hydrogen, methane, and VFAs profiles in 10 g/L BESA-amended batch cultures without pH adjustment 74

Figure 3-29. VFAs profiles in 10 g/L BESA-amended batch cultures without pH adjustment 75

Figure 3-30. Profiles of processed COD in 10 g/L BESA-amended batch cultures without pH adjustment 75

Figure 3-31. Cumulative hydrogen, methane, and VFAs profiles in batch cultures at initial pH 9 with 10 g/L BESA 77

Figure 3-32. VFAs profiles in batch cultures at initial pH 9 with 10 g/L BESA 78

Figure 3-33. Profiles of processed COD in batch cultures at initial pH 9 with 10 g/L BESA 78

Figure 3-34. Cumulative hydrogen, methane, and VFAs profiles in batch cultures at initial pH 5 with 10 g/L BESA 80

Figure 3-35. VFAs profiles in batch cultures at initial pH 5 with 10 g/L BESA 81

Figure 3-36. Profiles of processed COD in batch cultures at initial pH 5 with 10 g/L BESA 81

Figure 3-37. Observed butyric acid/acetic acid ratio under various operational conditions 82

Figure 3-38. Membrane-typed air diffuser used in this study 86

Figure 3-39. Cumulative hydrogen, methane, and VFAs profiles in semi-continuous flow membrane-coupled bioreactor fed with untreated digested sludge 89

Figure 3-40. Profiles of processed COD in semi-continuous flow membrane-coupled bioreactor fed with untreated digested sludge 89

Figure 3-41. Cumulative hydrogen, methane, and VFAs profiles in semi-continuous flow membrane-coupled bioreactor fed with heat-treated digested sludge 91

Figure 3-42. Profiles of processed COD in semi-continuous flow membrane-coupled bioreactor fed with heat-treated digested sludge 91

Figure 3-43. Cumulative hydrogen, methane, and VFAs profiles in semi-continuous flow membrane-coupled bioreactor fed with autoclaved digested sludge 93

Figure 3-44. Profiles of processed COD in semi-continuous flow membrane-coupled bioreactor fed with autoclaved digested sludge 93

Figure 3-45. Cumulative hydrogen, methane, and VFAs profiles in semi-continuous flow membrane-coupled bioreactor fed with autoclaved digested sludge at pH 5 95

Figure 3-46. Profiles of processed COD in semi-continuous flow membrane-coupled bioreactor fed with autoclaved digested sludge at pH 5 95

Figure 3-47. Hydrogen production rate in semi-continuous flow membrane-coupled bioreactor fed with autoclaved digested sludge at pH 5 96

Figure 3-48. Schematic diagram of PCR program 102

Figure 3-49. 16S rDNA of the isolated microorganisms 102

Figure 3-50. pGEMR-T Vector circle map and sequence reference points.(이미지참조) 103

Figure 3-51. RFLP analysis of 16S rDNA 105

Figure 3-52. T-RFLP analysis results 105

Figure 3-53. Confocal laser scanning microscopy (CLSM) micrograph of FISH of sludge sample (a) DAPI staining (Blue), (B) is showing beta proteobacteria hybridized by probe ALF 968 (Cy3-labelled, Green) (C) overlay, (D) phase-contrast image 108

Figure 3-54. FISH micrograph of culture sample obtained at the beginning (left) and the end (right) of incubation time with fluorescently labeled; α-, γ-proteobacteria hybridized by probe ALF968 (Cy5-labelled, Purple) and GAM42a (Cy3-labelled, Green) 109

Figure 3-55. Gas separation membrane (left) and carbon dioxide absorber (right) used for the hydrogen gas separation in this study 110

Figure 3-56. Extent of separated hydrogen purity using various carbon dioxide gas removal processes with gas separation membrane 111

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