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Ⅰ 실증규모 초임계수 설비를 이용한 목질계 바이오매스 당화 공정 개발 ······ 1
1.1. 실증규모 초임계수 당화설비 도입을 위한 예비실험 ······································ 3
1) 고압펌프 유입구에 가압 필요 ····································································· 4
2) 라인히터 보강 ····························································································· 4
3) 압력계 추가 설치 ························································································ 4
4) Drain Valve 설치 ························································································ 4
5) 분리기(필터) 부분에 By-Pass 라인 설치 ····················································· 5
6) 고압 피팅 사용 ··························································································· 5
1.2. 백합나무 목분 가수분해 반응 예비 실험 ······················································ 5
1.2.1. 백합나무를 활용한 가수분해 Lab. 장비 개요 ········································ 5
1.2.2. 초임계수 가수분해 반응 조건 ····························································· 6
1.3. 백합나무, 현사시나무, 리기다소나무를 활용한 가수분해 Lab. 실험 ·············· 7
1.4. 백합나무를 활용한 가수분해 Lab. 실험 ······················································ 12
1.4.1. 실험 장치 ··························································································· 12
1.4.2. 실험 조건 ··························································································· 12
1.4.3. 실험 결과 ··························································································· 12
1.5. 백합나무, 참나무, 리기다소나무, 낙엽송을 활용한 가수분해 Pilot 실험 ······ 14
1.5.1. 실험 장치 ··························································································· 14
1.6. 목분 가수분해 반응 예비 실험 결과의 반영 ··············································· 17
1.7. 실증규모 초임계수 당화설비 도입 ······························································· 19
1.7.1. 도입되는 실증규모 초임계수 당화설비의 구성 ···································· 19
1.7.2. 장비 설치 ·························································································· 20
1.7.3. 초기 장비 구성 및 개선 ····································································· 21
1.7.4. 초임계수 당화 시료 제조용 분쇄기 별도 도입 ···································· 22
1.8. 실증규모 초임계수 당화설비를 이용한 목분 당화 ······································· 22
1.8.1. 공시재료 채취 ····················································································· 22
1.8.2. 재료 및 방법 ······················································································ 23
1.8.3. 백합나무 목분의 바이오매스 당화 반응 결과 ······································ 25
1.9. 초임계수 당화의 당화효율 향상 ·································································· 27
1.10. 유동화제 첨가를 이용한 고농도 슬러리 당화 ············································ 29
1.11. 초임계수 당화설비 이용 정량적 당화율 분석 및 부산물 분석 ·················· 31
1.12. 고온고압수 처리에 의한 당화액의 발효 저해물질 저감 공정 개발 ············ 39
1.12.1. 다양한 상용 수지를 적용 당화액 내 주요 발효 저해물질 제거 ········ 40
1.12.2. 목탄을 이용한 초임계수 당화액의 발효저해물질 제거 ······················ 43
1.13. 초임계수 당화 부산물(당화잔사) 분석 ························································ 45
Ⅱ 목질계 당화액을 이용한 바이오에탄올 제조 ············································ 47
2.1. 황산가수분해 당화액 제조 ·········································································· 49
2.2. 바이오에탄올 제조시스템 개발 ···································································· 49
2.2.1. 자일로오스 발효를 위한 유전자 재조합 균주의 제조 ·························· 49
2.2.2. 표준당 발효를 통한 최적 발효 조건 탐색 ·········································· 53
2.3. 황산 이용 목질 당화액의 발효 ··································································· 54
2.3.1. 리기다소나무 제조 황산 당화액 에탄올 발효 ······································ 55
2.3.2. 백합나무이용 황산 당화액 에탄올 발효 ·············································· 56
2.4 초임계수 처리 당화액의 에탄올 발효 ·························································· 56
2.4.1. 염산 촉매 고온고압수(초임계수) 당화 ·················································· 56
2.4.2. 리기다소나무 모사 당화액을 이용한 에탄올 발효 ······························· 57
2.4.3. 리기다소나무 당화액을 모사한 배지제조 및 발효 ······························· 59
2.4.4. 리기다소나무 당화액 헤미셀를로오스 조성 모사배지 발효 ·················· 61
2.5. 초임계수 처리 백합나무 당화액을 이용한 에탄올 발효 ······························ 63
2.5.1. 백합나무 당화액 조성 성분 확인 ························································ 63
2.5.2. 백합나무 초임계수 당화액의 모사 배양액을 이용한 에탄올 발효 ······· 64
2.5.3. 백합나무의 산 촉매 하 초임계수 처리 당화액의 재당화 ····················· 66
2.6. Acetic acid 저항성 바이오에탄올 제조시스템 개발 ···································· 68
2.7. 무촉매와 질산촉매 고온고압수처리 당화액의 에탄올 발효 ·························· 71
Ⅲ 급속열분해 이용 바이오오일의 연료특성 연구 ········································· 73
3.1. 급속열분해 이용 백합나무의 바이오오일 제조 ············································ 75
3.2. 백합나무 목분의 열분해 거동 조사 ····························································· 76
3.3. 반응온도별 백합나무 바이오오일 생산 특성 조사 ······································· 77
3.4. 반응시간 변화에 따른 바이오오일 수율 변화 ·············································· 78
3.5. 백합나무 목분의 입도별 바이오오일 제조 ··················································· 79
3.6. 백합나무 바이오오일의 주요 성분 분석 ······················································ 81
3.7. 급속열분해 이용 바이오오일 최적 제조 조건 탐색 ····································· 85
3.8. 급속열분해 온도 조건별 바이오오일의 수분, 발열량, 원소분석 및 pH 변화 ····· 87
3.9. 반응표면 분석법을 이용한 바이오오일 생산 조건 최적화 ··························· 88
3.10. 시료 성상별 급속열분해 및 바이오오일 제조 특성 ··································· 90
3.11. 감압증류 온도변화에 의한 바이오오일의 특성 변화 ·································· 94
3.12. 유동층 모래 및 촉매 혼합에 의한 연료특성 구명 ····································· 97
3.12.1. 유동층의 모래 및 촉매 구성 ····························································· 97
3.12.2. 유동층 변화에 따른 바이오오일 특성 ··············································· 97
Ⅳ 무기성분이 급속열분해 및 바이오오일에 미치는 영향 ··························· 101
4.1. 칼륨(K)이 급속열분해 및 바이오오일 특성에 미치는 영향 ························ 103
4.1.1. 바이오매스 내 화학 조성 분석 ························································· 103
4.1.2. 바이오매스 내 무기성분 정량 ··························································· 104
4.1.3. 시료 열중량 및 열분해 산물 분석 (Thermogravimetric analysis) ······ 105
4.1.4. 바이오오일의 저장성 평가 ································································ 112
4.2. 마그네슘이 급속열분해 및 바이오오일 특성에 미치는 영향 ······················ 114
4.2.1. 열중량 및 열분해 산물 분석 ····························································· 116
Ⅴ 촉매처리에 의한 바이오오일 연료 성능 개선 ········································ 129
5.1. 바이오매스의 촉매열분해 ·········································································· 131
5.1.1. 메조포러스 촉매 및 시료 특성 분석 ················································· 131
5.1.2. 산림바이오매스의 무촉매 열분해 ······················································ 133
5.1.3. 고정층 반응기를 이용한 촉매 열분해 ··············································· 136
5.2. 바이오오일의 수소첨가탈산소 반응 ··························································· 147
5.2.1. Guaiacol의 수소첨가탈산소화 반응 ··················································· 147
5.2.2. 압력에 따른 guaiacol의 전환율 및 주요 생성물질 수율 ··················· 147
5.2.2. 실제 바이오오일의 수소첨가탈산소화 반응 ······································· 148
5.3. 바이오오일과 알코올의 혼합에 따른 pH, 수분 및 발열량 변화 ················ 150
5.4. 반탄화 굴참나무의 열분해/촉매열분해 ······················································· 151
5.4. 반탄화 굴참나무의 촉매 열분해 ································································ 156
5.5. 바이오오일의 수소첨가탈산소화 반응 ························································ 160
참고문헌 ············································································································· 165