표제지

제출문

보고서 요약서

요약문

SUMMARY

CONTENTS

목차

제1장 연구개발과제의 개요 18

제1절 연구의 목적 18

제2절 연구의 필요성 19

제2장 국내외 기술개발 현황 22

제1절 국내기술의 현황 22

제2절 선진국의 기술 현황 28

제3장 연구개발수행 내용 및 결과 36

제1절 부산석고로부터 광물탄산화 36

제2절 경량 콘크리트를 이용한 광물탄산화 연구 45

제3절 폐콘크리트 미분말의 CO₂ 고용화 방법 65

제4절 액티놀라이트를 이용한 광물탄산화 73

제5절 부산석고를 이용한 CO₂ 고정화 기술 80

제6절 실시간 X-선 회절법을 이용한 광물탄산화 반응의 기작 연구 (위탁연구-1) 91

제7절 전기로제강슬래그 배출특성 및 CO₂가스 고정화기술 기초연구 (위탁연구-2) 102

제8절 화력발전소 부산물 배출특성 및 CO₂ 가스 고정화기술 기초 연구 (위탁연구-3) 137

제4장 목표달성도 및 관련분야에의 기여도 153

제1절 연도별 연구목표 153

제2절 연구개발목표의 달성도 154

제5장 연구개발결과의 활용계획 155

제1절 기술적 측면 155

제2절 경제·산업적 측면 155

제3절 정책적 측면 156

제4절 산업화 방안 156

제6장 연구개발과정에서 수집한 해외과학기술정보 161

제7장 참고문헌 162

Table 2-1. Technical level of the domestic mineral carbonation compared with advanced countries. 23

Table 2-2. Mineral types investigated for carbonation in research papers and reports (2005-2007; Sipila et al., 2008) 25

Table 2-3. Materials (synthetic) investigated in research papers and reports (2005-2007; Sipila et al., 2008) 26

Table 2-4. Solid residue materials investigated for carbonation purposes (two left columns) and references not related to specific mineral studies (see comment column) in research papers and reports published 2005-07(Sipila et al., 2008) 27

Table 2-5. Various processes of mineral carbonation developed until now. 30

Table 2-6. Optimum carbonation conditions and extent of carbonation after 1h (Gerdemann et al., 2007; O'/Connor et al., 2004) 31

Table 3-1-1. Occurrence and recycling of industrial gypsum. 37

Table 3-1-2. Chemical composition of chemical gypsum. 39

Table 3-1-3. Trace elements analysis of chemical gypsum. 39

Table 3-1-4. Experimental results of mineral carbonation by industrial gypsum. 41

Table 3-1-5. Aanalytical result of major element of calcite and ammonium sulfate as a product of mineral carbonation. 42

Table 3-1-6. Aanalytical result of trace element of calcite and ammonium sulfate as a product of mineral carbonation. 42

Table 3-2-1. Materials of autoclaved lightweight concrete. 46

Table 3-2-2. Chemical Composition of ALC as a starting material. 47

Table 3-2-3. Mineral assemblages of ALC with heating. 47

Table 3-2-4. Maximum value for the formation of carbonates from tobermorite and ALC. 50

Table 3-2-5. Results of mineral carbonation from various conditions in room temperature. 51

Table 3-2-6. Results of mineral carbonation from various conditions in warm condition. 52

Table 3-2-7. Results of mineral carbonation formed with reaction time. 54

Table 3-2-8. Results of mineral carbonation formed with pH. 56

Table 3-2-9. Conditions and mineral assemblages of the specimens through the mineral carbonation in the closed system. 62

Table 3-5-1. 석고와 이산화탄소 반응에서 주요물질들의 물리 화학적 특성. 81

Table 3-7-1. IPCC CO₂ emission scenario. 102

Table 3-7-2. Chemical compositions of samples. 111

Table 3-8-1. Coal-fired power plants of Korea in 2009. 137

Table 3-8-2. Coal ash production and recycling rate (2004 ~ 2005). 139

Table 3-8-3. Coal ash production of D-power plant. 139

Table 3-8-4. Chemical compositions of FA samples from XRF analysis. 140

Table 3-8-5. Chemical compositions of B-plant FA with two blaine values. 141

Table 3-8-6. Variation of cations concentrations with leaching time 145

Table 5-4-1. Some industrial residues for the mineral carbonation showing the contents alkalic components, rate of carbonation and amounts of fixation of CO₂. 157

Table 5-4-2. Starting materials and the products for the carbonation reaction in the case of gypsum. 158

Table 5-4-3. The relation of the amount of CO₂ mitigation and starting materials, product, reactor size, etc for the calculation of P&ID. 158

Table 5-4-4. Expecting candidates for the industralization of the mineral carbonation technique. 159

Fig. 2-1. Direct gas-solid reaction times achieved for complete carbonation (kinetic control) at various carbonation conditions of 74-125㎛ particles at TKK, Finland (Sipila et al., 2008). 32

Fig. 2-2. Schematic illustration of a CaCO₃ production process from waste cement (Katsuyama et al., 2005). 34

Fig. 3-1-1. Schematic diagram of the carbonation reaction system. 1) Bomb of CO₂ 2) Flow meter, 3) pH meter 4) Thermocouple 5) Glass Reactor body, 6) cover plate, 7) stirrer, 8) Temperature controller 38

Fig. 3-1-2. XRD Patterns of starting material gypsum, calcite and vaterite(vaterire) as a Product of mineral carbonation. 43

Fig. 3-1-3. SEM image of calcite and vaterite as a product of mineral carbonation. 44

Fig. 3-2-1. XRD pattern of autoclaved lightweight concrete. 46

Fig. 3-2-2. The change of mineral assemblages of ALC with heating. 48

Fig. 3-2-3. DTA/TG diagram of ALC. 48

Fig. 3-2-4. Process of mineral carbonation from autoclaved lightweight concrete. 49

Fig. 3-2-5. XRD patterns of products with various processes in room temperature. 51

Fig. 3-2-6. XRD patterns of products with various processes in warm condition. 53

Fig. 3-2-7. XRD patterns of products formed with reaction time. 55

Fig. 3-2-8. XRD patterns of products formed with pH. 56

Fig. 3-2-9. FE-SEM image of the raw material. 57

Fig. 3-2-10. Mapping images of the specimen from the mineral carbonation (SEQ-7). 58

Fig. 3-2-11. Mapping images of the specimen from the mineral carbonation (SEQ-9). 58

Fig. 3-2-12. Mapping images of the specimen from the mineral carbonation (SEQ-16). 59

Fig. 3-2-13. Reaction procedure of the mineral carbonation in the closed system. 60

Fig. 3-2-14. Reaction vessel using for the mineral carbonation in the closed system. 60

Fig. 3-2-15. XRD patterns of specimens synthesized with reaction time in the closed system. 63

Fig. 3-2-16. The species of carbon existing in the reaction solution. 64

Fig. 3-3-1. 시멘트 미분말의 CO2 가스의 탄산화 반응에 따른 시멘트 미분말 광물상의 X-ray 회절 피크. 68

Fig. 3-3-2. CO₂ 탄산화 방법에 따른 시멘트 미분말의 CO₂ 탄산화율. 69

Fig. 3-3-3. 수화 반응된 시멘트 미분말과 CO₂ 탄산화 방법에 따른 시멘트 미분말의 주사현미경 사진 70

Fig. 3-3-4. 시멘트 미분말과 수화 반응된 시멘트 미분, CO₂ 탄산화된 시멘트 미분말, 폐콘크리트 폐시멘트 미분말의 Sia29 NMR 스펙트럼(이미지참조) 71

Fig. 3-3-5. CO₂ 탄산화 된 폐시멘트 미분말의 열분해 곡선 72

Fig. 3-4-1. The crystal structure of amphibole. 74

Fig. 3-4-2. The schematic diagram of hydrothermal apparatus. 74

Fig. 3-4-3. The procedure of the mineral carbonation. 76

Fig. 3-4-4. XRD patterns of the reaction results with time. (a) actinolite (b) 24hr (c) 48hr (d) 72hr. 76

Fig. 3-4-5. XRD patterns of at various temperature (a) 100℃, 9days, CO₂ 60bar (b) 270℃, 48hr, CO₂ 20bar (c) 290℃, 48hr, 5bar 78

Fig. 3-4-6. XRD patterns at various pH (a) actinolite (b) pH2 (c) pH 11, (d) 0.5M NaHCO₃ 78

Fig. 3-4-7. FE-SEM image of actinolite and synthetic product. 79

Fig. 3-5-1. 석고와 이산화탄소로부터 황산암모늄 및 탄산칼슘 생성(생상)공정 디자인. AS: ammonium sulfate, CaSO₄, AC: ammonium carbonate, (NH₄)₂CO₃ CC: calcium carbonate, CaCO₃, CS: calcium sulfate,... 86

Fig. 3-6-1. 본 실험의 시료로 사용된 scolecite의 구조 모델. (a) Si(파란색)과 AI(하늘색)으로 구성된 5개의 사면체(T5O10)로 이루어진 기본 적층단위 (building unit)... 93

Fig. 3-6-2. 본 실험의 시료로 사용된 zeolite-LTL의 구조모델. (a) 기본 적층단위인 cancrinite cage의 구조. cancrinite cage는 18개의 규소 4면체로 구성되어 있으며, 중심부에 3회전축을 형성한다.... 94

Fig. 3-6-3. 5A 빔라인 내부 고온 실험 셋팅 모습. 히터는 외부의 온도 컨트롤러에 의해 제어됨 95

Fig. 3-6-4. 본 실험을 위해 설계된 분배기. 밸브 조작에 의해 진공을 유지한 상태로 CO₂ 주입이 가능하다 96

Fig. 3-6-5. 액체질소 환경 하에서의 DAC 시료 삽입. 우 하단의 그림과 같이 다이아몬드 압력 셀 전체가 저온을 유지하게 하여 CO₂가 gas 변하여 공기 중으로 사라지는 것을 막... 97

Fig. 3-6-6. 온도변화에 따른 scolecite의 실시간 X-ray 회절 패턴의 변화 양상 98

Fig. 3-6-7. 온도변화에 따른 zeolite-LTL의 실시간 X-ray 회절 패턴의 변화 양상, 하단의 빨간색 라인은 가열 후 다시 냉각 하여 상온으로 돌아왔을 때의 회전패턴 임. 99

Fig. 3-6-8. CO₂를 매개로한 압력 하에서의 scolecite 의 회절패턴 변화 양상. 99

Fig. 3-6-9. 압력에 따른 scolecite의 각 축 길이의 변화. (a) a축(빨간색)과 b(파란색)의 길이변화를 도시함., (b) c축 길이의 변화 100

Fig. 3-6-10. 압력에 따른 scolecite의 부피변화 비 (normalized volume). 100

Fig. 3-6-11. 압력에 따른 zeolite-LTL의 회절패턴 변화 양상. 101

Fig. 3-7-1. Multi-step process for carbonating calcium silicates using acetic acid. 106

Fig. 3-7-2. CaCO₃ production process from waste. cement. 106

Fig. 3-7-3. flow diagram of pH-swing process. 107

Fig. 3-7-4. Experimental dissolution system. 111

Fig. 3-7-5. Effect of leaching temperature on the extraction of Ca from the electric arc furnace slag(33.3 wt% CH₃COOH, 120㎛, 400rpm). 113

Fig. 3-7-6. Effect of leaching temperature on the extraction of Ca from the electric arc furnace slag(2N HCl, 120㎛, 400rpm). 113

Fig. 3-7-7. wt% Ca in leaching residues. 114

Fig. 3-7-8. Effect of leaching temperature on the extraction of Fe from the electric arc furnace slag(33.3 wt% CH₃COOH, 120㎛, 400rpm). 115

Fig. 3-7-9. Effect of leaching temperature on the extraction of Fe from the electric arc furnace slag(2N HCl, 120㎛, 400rpm). 115

Fig. 3-7-10. Effect of leaching temperature on the extraction of Si from the electric arc furnace slag(33.3 wt% CH₃COOH, 120㎛, 400rpm). 116

Fig. 3-7-11. Effect of leaching temperature on the extraction of Si from the electric arc furnace slag(2N HCl, 120㎛. 400rpm). 117

Fig. 3-7-12. Effect of acetic acid concentration in the extraction of Ca from the electric arc furnace slag(70℃, 120㎛, 400rpm). 118

Fig. 3-7-13. Effect of hydrochloric acid concentration in the extraction of Ca from the electric arc furnace slag(70℃, 120㎛, 400rpm). 118

Fig. 3-7-14. Effect of acetic acid concentration in the extraction of Fe from the electric arc furnace slag(70℃, 120㎛, 400rpm). 119

Fig. 3-7-15. Effect of hydrochloric acid concentration in the extraction of Fe from the electric arc furnace slag(70℃, 120㎛, 400rpm). 120

Fig. 3-7-16. Effect of acetic acid concentration in the extraction of Si from the electric arc furnace slag(70℃, 120㎛, 400rpm). 121

Fig. 3-7-17. Effect of hydrochloric acid concentration in the extraction of Si from the electric arc furnace slag(70℃, 120㎛, 400rpm). 121

Fig. 3-7-18. Effect of particle size on the extraction of Ca from the electric arc furnace slag (50℃, 33.3 wt% CH₃COOH, 120㎛, 400rpm). 123

Fig. 3-7-19. Effect of particle size on the extraction of Ca from the electric arc furnace slag (50℃, 2N HCl, 120㎛, 400rpm). 123

Fig. 3-7-20. Effect of particle size on the extraction of Fe from the electric arc furnace slag (50℃, 33.3 wt% CH₃COOH, 120㎛, 400rpm). 124

Fig. 3-7-21. Effect of particle size on the extraction of Fe from the electric arc furnace slag (50℃, 2N HCl, 120㎛, 400rpm). 125

Fig. 3-7-22. Effect of particle size on the extraction of Si from the electric arc furnace slag (50℃, 33.3 wt% CH₃COOH, 120㎛, 400rpm). 126

Fig. 3-7-23. Effect of particle size on the extraction of Si from the electric arc furnace slag (50℃, 2N HCl, 120㎛, 400rpm). 126

Fig. 3-7-24. Effect of leaching time on the extraction of Ca from the electric arc furnace slag (33.3 wt% CH₃COOH, 120㎛, 400rpm). 128

Fig. 3-7-25. Effect of leaching time on the extraction of Ca from the electric arc furnace slag (2N HCl, 120㎛, 400rpm). 128

Fig. 3-7-26. Effect of leaching time in the extraction of Fe from the electric arc furnace slag (33.3 wt% CH₃COOH, 120㎛, 400rpm). 130

Fig. 3-7-27. Effect of leaching time in the extraction of Fe from the electric arc furnace slag (2N HCl, 120㎛, 400rpm). 130

Fig. 3-7-28. wt% Fe in residues (4hr). 131

Fig. 3-7-29. Effect of leaching time on the extraction of Si from the electric arc furnace slag (33.3 wt% CH₃COOH, 120㎛, 400rpm). 132

Fig. 3-7-30. Effect of leaching time on the extraction of Si from the electric arc furnace slag (2N HCl, 120㎛, 400rpm). 132

Fig. 3-7-31. Proposed process to raise pH and to recycle unreacted acid in carbonation procedure. 135

Fig. 3-8-1. Wastes from coal-fired power plant. 138

Fig. 3-8-2. FGD and DeNOx process and coal ash in power plant (from KOPEC). 138

Fig. 3-8-3. SEM images of FA samples (a: D09 FA, b: H09 FA). 141

Fig. 3-8-4. SEM images of cenosphere occurrence. 142

Fig. 3-8-5. XRD Pattern of fly ashes with leaching. 142

Fig. 3-8-6. Conceptual process for CO₂ fixation using coal ash. 143

Fig. 3-8-7. pH variation with time. 144

Fig. 3-8-8. SEM images and EDX analysis. 146

Fig. 3-8-9. EDX analysis of needle-like crystals upon fly ash after leaching. 147

Fig. 3-8-10. Apparatus for VLE(Vapor-Liquid Equilibrium). 148

Fig. 3-8-11. CO₂ absorption with various temperature under 6 bar. 149

Fig. 3-8-12. CO₂ absorption with various temperature under 12 bar. 150

Fig. 3-8-13. An example of C2SEA R reactor in LLNL.(이미지참조) 151

Fig. 3-8-14. CO₂ storage process by mineral carbonation with coal ash. 152