[보고서]알칼린계 산업부산물의 광물탄산화 연구

이승우

알칼린계 산업부산물의 광물탄산화 연구
Study on the Mineral Carbonation of Alkaline Industrial Products 원문보기

보고서 정보
주관연구기관	한국지질자원연구원 Korea Institute of Geoscience and Mineral Resources
연구책임자	이승우
참여연구자	방준환 , 최병영 , 장영남 , 채수천 , 박상원 , 이선혜 , 전치완 , 조환주 , 송경선
보고서유형	연차보고서
발행국가	대한민국
언어	한국어
발행년월	2015-12
과제시작연도	2015
주관부처	미래창조과학부 KA
사업 관리 기관	한국지질자원연구원 Korea Institute of Geoscience and Mineral Resources
등록번호	TRKO201600000637
과제고유번호	1711027258
DB 구축일자	2016-04-23
키워드	광물탄산화,이산화탄소,슬래그,알칼리 토금속,탄산칼슘Mineral carbonation,CO₂,Slag,Alkaline earth metal,CaCO₃

초록 ▼

최종(연차)목표
● 산업부산물 및 자연산 광물을 이용하여 이산화탄소 저감기술 개발
● 알칼린계 금속 추출방법과 탄산화 기술 최적화
● 산업부산물로부터 추출된 칼슘 및 마그네슘 추출제 재활용 및 생성물의 고부가가치화
● 부가가치 탄산화과정 생성물 생산으로 산업적 활용성 증대 및 경제성 확보

개발내용 및 결과
● 암모늄 및 유/무기산 이용 자연산 및 산업부산물로부터 알칼리 토금속 추출기술 개발
● 물리적, 화학적 방법을 이용한 추출 용제 재활용
● 산업부산물 및 자연산 광물에서 다양한 전처리 방법을 이용하여 알칼린계 금속을 분리하고 탄산화 기술을 적용하여 고순도 탄산염광물 생성
● 고부가가치 탄산화 물질 합성 공정 개발

기대효과
● 산업부산물 및 자연산 광물을 이용하여 친환경적으로 CO₂ 가스 저감
● 산업부산물 및 미이용 자연산 광물의 순환 활용
● 광물탄산화 과정으로 생성되는 탄산염광물을 고부가가치 용도로 활용함에 따라 경제성 제고 효과

적용분야
● 이산화탄소 배출 산업: 제철소, 발전소, 시멘트 분야
● 탄산화물질 활용 산업: 제지, 페인트, 플라스틱 등

Abstract ▼

The Efficiency of calcium extraction from granulated slag showed range from 22.8-32.2 wt.% and maximum efficiency of calcium extraction was 53.0 wt.%. NH₄NO₃ and NH4Cl were suitable as solvent of calcium extraction. The calcium of approximately 95 wt.% in extracted solution was transformed into calcite. Consequently, amount of carbon dioxide sequestration was affected from efficiency of calcium extraction. The maximum extraction rate was 79% when the strong acid was used. However, the ammonia group solvents did not reach the 50%. Especially, amount of calcium ions extraction did not have any great difference in total calcium concentration viewpoint.
Therefore, we think that solid-liquid ratio study need to consider the additional work because the future work will be used to carbon dioxide gas.
We have performed the extraction of cations such as calcium for mineral carbonation of blast furnace slag using aqueous acetic acid solution at room temperature and atmosphere pressure. After leaching, separation of acetic acid was attempted to identify the possibility of recycling of acetic acid solvent via layer crystallization method.
Magnesium extraction of serpentine was carried out under experimental conditions (reaction temperature: 300℃ and ratio of serpentine per extracted solution: 66 at room temperature). The NH₄⁺ rich solution after extraction was reused for pH swing process. The carbonates materials including MgCO₃ and CaCO₃ could be synthesized via pH swing process.
Alkaline pulp and paper mill waste sludges produced by primary pulping operation or waste paper making representing an environmental and disposal problem manufacturers of pulp and paper. Paper sludge has traditionary disposed of by landfilling, compositing and incineration generally largely or totally wasted. The extent of acid extraction/solubilization of the inorganic and organic components in the paper making sludge depends on conditions of the sludge treatment with acids, nature of the acid, the acid concentration, and contact time with the acid in particular.
The pulp and paper sludges collected domestic area and their bulk content, major components and mineralogical structures was estimated. Several acids, such as Hydrochloric acid, nitric acid, sulfuric acid and acetic acid, was treated in the condition of varied experimental conditions for the purpose of solubilization the pulp and paper sludges. Obtained results showed primary diminished amount of sludges above 80%, and the residuals became possible waste to energy.
The process of calcium carbonate film synthesis has been studied. First, the hemispherical shape of the amorphous CaCO₃ phase was formed at the interface between a water solution including Ca(OH)₂ and air. Subsequently, the CaCO₃ (calcite) film crystallized based on the self-aggregation of the amorphous CaCO₃. This experiment was simulated with a geochemical model to calculate the ion concentration of calcium and bicarbonate during the reaction, and the effect of temperature on carbonate synthesis was tested.
Patent on CO₂ mineralization applied in U.S. during the years of 2001-2015 was analysed using data from KISTI, KIPO, and WIPS. The analysis showed that Clera Corporation is a core competitor to be a benchmark. In addition, it was promised technologies for CO₂ mineralization that the methods for pH adjustment for CO₂ mineralization, the use of various metal ions, the methods for selective metal ion uptake, and the methods for CO₂ dissolution in the metal ions containing solutions.
The secondary phase mineral formation associated with the microbial Fe-respiration of structural Fe(III) of nontronite. The secondary phase minerals such as vivianite, siderite and calcite was detected may have resulted from dissolution of bioreduced smectite associated with microbial Fe(III) reduction and interlayer cation exchange process. However the specific mechanism and its optimum conditions were yet to be clearly explained. In the present study we investigate the chemical modification of nontronite during the biogenic reduction as well as changes in concentration of structural metals in the supernatant to give an explanation for secondary phase mineral formation with 'reductive dissolution'. The batch experiment as well as field work in particular, may have many fields that can be applied to scale-up experiment of CO₂ trap/modeling study. In fact, the role of microbial activity in carbonate minerals, and the optimum conditions for the microbial calcification could be the important preliminary data applicable to CO₂ modeling research.

목차 Contents

표지 ... 1
제출문 ... 2
연차보고서 요약서 ... 4
요약문 ... 5
SUMMARY ... 11
CONTENTS ... 14
목차 ... 17
표목차 ... 20
그림목차 ... 25
제 1 장 연구개발과제의 개요 ... 32
제 1 절 연구의 목적 ... 32
제 2 절 연구의 필요성 ... 33
1. 기술적 측면 ... 33
2. 경제·산업적 측면 ... 33
제 2 장 국내외 기술개발 현황 ... 36
제 1 절 국내 기술 현황 ... 36
1. 국내 기술 동향 ... 36
2. 국외 기술 수준 ... 37
제 2 절 국외 기술 현황 ... 38
제 3 장 연구개발수행 내용 및 결과 ... 44
제 1 절 고로슬래그 (수재)로부터 칼슘 추출 및 탄산화 실험 ... 44
1. 서론 ... 44
2. 실험 재료 및 실험방법 ... 46
3. 결과 및 검토 ... 50
4. 결론 ... 63
제 2 절 고로슬래그 (괴재)로부터 칼슘 추출 ... 64
1. 서론 ... 64
2. 실험방법 ... 68
3. 결과 및 검토 ... 71
4. 결론 ... 83
제 3 절 페로니켈 슬래그로부터 마그네슘 ... 84
1. 서론 ... 84
2. 폐로니켈 슬래그의 특성 ... 86
3. 실험방법 ... 91
4. 결과 ... 95
5. 고찰 ... 99
6. 결론 ... 103
제 4 절 고로슬래그로부터 칼슘 추출 및 용매회수 ... 105
1. 서론 ... 105
2. 실험방법 ... 106
3. 결과 및 검토 ... 110
4. 결론 ... 125
제 5 절 사문석이용 마그네슘 추출 및 용매회수 ... 126
1. 서론 ... 126
2. 실험방법 ... 126
3. 결과 및 검토 ... 129
4. 결론 ... 139
제 6 절 제지슬러지의 분해 및 탄산화 ... 149
1. 서론 ... 149
2. 실험 ... 152
3. 결과 및 고찰 ... 154
4. 결언 ... 167
제 7 절 탄산칼슘 막 합성 및 특성 연구 ... 168
1. 서론 ... 168
2. 실험방법 ... 169
3. 결과 및 검토 ... 172
4. 결론 ... 184
제 8 절 지구화학 모델을 이용한 사문석 반응모사 ... 185
1. 서론 ... 185
2. 모델링 방법 ... 186
3. 결과 및 검토 ... 190
4. 결론 ... 194
제 9 절 특허 맵 ... 195
1. 특허 맵 정의 ... 195
2. 특허 맵 작성 ... 196
3. 특허조사 및 분석결과 ... 197
4. 결론 ... 236
제 10 절 박테리아에 의한 탄산염광물 형성 및 구조 특이성 분석 ... 239
1. 서론 ... 239
2. 국내외 기술 개발 현황 ... 241
3. 연구개발수행 내용 및 결과 ... 244
4. 연구개발목표 달성도 및 대외기여도 ... 262
5. 연구개발결과의 활용계획 ... 265
제 11 절 직접 수성 방법에 의한 레드 머드와 슬레이트 혼합물의광물탄산화 특성 연구 ... 269
1. 서론 ... 269
2. 국내외 연구 동향 ... 271
3. 실험 방법 ... 272
4. 실험 결과 및 고찰 ... 275
5. 결론 ... 289
참 고 문 헌 ... 290
끝페이지 ... 304

표/그림 (108)

표 Fig. 2-2-1. Direct mineral carbonation is accomplished in one step, while indirect mineral carbonation is conducted in two or more steps. Note M refers to either calcium (Ca) or magnesium (Mg).
표 Fig. 3-1-1. Schematic diagram of indirect carbonation from granulated slag
표 Fig. 3-1-2 XRD result of granulated slag
표 Fig. 3-1-3. Efficiency of extracted calcium from granulated slag in solvents
표 Fig. 3-1-4. XRD result of granulated slag after extraction (Fig. 1 내 solid 1)
표 Fig. 3-1-5. Comparison of extracted calcium efficiency based on independent variable
표 Fig. 3-1-6. Maximum efficiency of extracted calcium
표 Fig. 3-1-7. Efficiency of extracted calcium from blast furnace slag in solvents
표 Fig. 3-1-8. Efficiency of extracted calcium from the pretreated blast furnace slag
표 Fig. 3-1-9. XRD result of carbonate obtained from carbonation of extracted calcium
표 Fig. 3-1-10. SEM images of carbonate obtained from carbonation of extracted calcium
표 Fig. 3-1-11. Trace of calcium weight in total experiment
표 Fig. 3-2-1. CO2 capture and utilization by using the alkaline waste (IPCC, 2005)
표 Fig. 3-2-2. mineral carbonation process when the ammonium solvent was used (J. Fagerlund et al., 2012)
표 Fig. 3-2-3. extraction experimental apparatus
표 Fig. 3-2-4. XRD result of BF slag A
표 Fig. 3-2-5. XRD result of air cooled BF slag
표 Fig. 3-3-1. Occurrences of ultramafic rocks in New Caledonia (Cho et al., 2011)
표 Fig. 3-3-2. Process of the production of Fe-Ni.
표 Fig. 3-3-3. Occurrences of ultramafic rocks in New Caledonia (Cho et al., 2011).
표 Fig. 3-3-4. Olivine structure. Open circles: oxygen, Black and grey solid circles: Mg or Fe, Small solid circle: silicon
표 Fig. 3-3-5. Structure of enstatite
표 Fig. 3-3-6. Precipitation pHs of the metal hydroxides with metal concentration.
표 Fig. 3-3-7. Activation of the Fe-Ni slag using various ammonium sulfates
표 Fig. 3-3-8. Extraction and precipitation rates.
표 Fig. 3-3-9. Combined diagram of Bowen reaction series and Goldich stability series.
표 Fig. 3-3-10. XRD patterns of the residue products from activation to final precipitation.
표 Fig. 3-4-1. Column for layer crystallization and sweating operatstion.
표 Fig. 3-4-2. Solid-liquid equilibrium of acetic acid and water mixture.
$Fig. 3-4-3. XRD diffractogram of blast furnace slag.$ 표 Fig. 3-4-3. XRD diffractogram of blast furnace slag.
표 FIg. 3-4-4. Dissolution of blast furnace slag in aqueous solution of acetic acid at room temperature.
표 Fig. 3-4-5. Extraction of Ca from blast furnace slag using 5 vol.% acetic acid
표 Fig. 3-4-6. (a) Si-rich gel formation in extracted solution and (b) dried after filtering (a) uisng 0.2 ㎛ membrane filter.
표 Fig. 3-4-7. Atomic depth profile of gel product obtained from extracted solution using acetic acid.
$Fig. 3-4-8. XRD diffractogram of slag residual after extracted using 85 vol% acetic acid.$ 표 Fig. 3-4-8. XRD diffractogram of slag residual after extracted using 85 vol% acetic acid.
$Fig. 3-4-9. XRD diffractogram of slag residual after extracted using 85 vol% acetic acid.$ 표 Fig. 3-4-9. XRD diffractogram of slag residual after extracted using 85 vol% acetic acid.
$Fig. 3-4-10. XRD diffractogram of carbonated product using 1 M monoethanolamine.$ 표 Fig. 3-4-10. XRD diffractogram of carbonated product using 1 M monoethanolamine.
표 Fig. 3-4-11. FE-SEM images of carbonated product using 1 M monoethanolamine.
표 Fig. 3-5-1. Extraction system of alkaline earth metal ion (water bath, reactor including stirrer, N2 gas)
표 Fig. 3-5-2. Results of Mg extraction according to experimental factor, (a) Temperature, (b) Ratio of serpentine/ extracted solution, (NH4)2SO4
표 Fig. 3-5-3. pH value according to reaction temperature..
표 Fig. 3-5-4. photos after and before extraction, (a) slurry solution including serpentine before extraction, (b) slurry solution after extraction at 200 ℃, (c) slurry solution after
표 Fig. 3-5-5. Extraction yield of mganesium (experimental condition: 2mol ammonium sulfate,
표 Fig. 3-5-6. XRD pattern of serpentine after Mg extraction
표 Fig. 3-5-7. The pH swing process on serpentine and BF slag. The concept of this process is that the reuse of NH +4 rich solution for carbonation.
표 Fig. 3-5-8. FE-SEM images after carbonation by using pH swing process. (a) and (b) are carbonation result of serpentine and white arrow in Fig. 3-5-8a means sphere. (c) and (d)
표 Fig. 3-6-1. Kraft pulp mill chemical recovery circuit of alkaline paper mill waste.
표 Fig. 3-6-2. XRD spectra of dried in the room temperature paper mill waste sludges, 1. Moolim, 2. Hankook, 3. Seah, 4. Ahjin.
표 Fig. 3-6-3. TGA profile of 1. Moolim paper mill waste sludge.
표 Fig. 3-6-4. TGA profile of 1. Moolim paper mill waste sludge.
표 Fig. 3-6-5. TGA profile of 2. Hankook paper mill waste sludge.
표 Fig. 3-6-6. TGA profile of 3. Seah paper mill waste sludge.
표 Fig. 3-6-6. TGA profile of 4. Ahjin paper mill waste sludge.
표 Fig. 3-6-7. FT-IR spectrum of 1. Moolim paper mill waste sludge.
표 Fig. 3-6-8. FT-IR spectrum of 2. Hankook paper mill waste sludge.
표 Fig. 3-6-9. FT-IR spectrum of 3. Seah paper mill waste sludge.
표 Fig. 3-6-10. FT-IR spectrum of 4. Ahjin paper mill waste sludge.
표 Fig. 3-6-11. Designed scheme of lab-scale paper mill waste sludge treatment processing system.
표 Fig. 3-7-1. Schematic illustration of experimental equipments. reactor (beaker, 2L) including Ca(OH)2 and water (a), electrode (b) and pH meter (c) for pH detection, and computer (d). In this experiment, atmospheric CO2 was spontaneously dissolved in the Ca(OH)2 solution.
표 Fig. 3-7-2. Schematic diagram of CaCO3 film formation modeling from Ca(OH)2 solution.
표 Fig. 3-7-3. pH detection on CaCO3 film formation. X axis is retention time for CaCO3 film formation and Y axis is pH value. The black star means boundary zone of CaCO3 formation range from 72 hr to 80 hr. The character (⊥) is sampling time for surface morphology
표 Fig 3-7-4. Schematic illustration of CaCO3 film formation. The direction of black star means the increase of retention time. RD is relative density
표 Fig. 3-7-5a. SEM images. retention time (1 hr) (a, scale bar: 20 ㎛), (b, scale bar: 5 ㎛) and retention time (8 hr) (c and d, scale bar: 5 ㎛).
표 Fig. 3-7-5b. SEM images. retention time (60 hr) (e and f, scale bar: 10 ㎛), (g, scale bar: 1 ㎛) and (h, scale bar: 500 nm).
표 Fig. 3-7-5c. SEM images. retention time (80 hr) (i, scale bar: 10 ㎛), (l, scale bar: 3 ㎛) and retention time (120 hr) (k, scale bar: 10 ㎛) (j, scale bar: 1 ㎛).
표 Fig. 3-7-5d. SEM images. retention time (430 hr) (m, scale bar: 100 ㎛), (n, scale bar: 10 ㎛), (o, scale bar: 10 ㎛), (p, scale bar: 5 ㎛).
표 Fig. 3-7-6. pH value vs. consumed CO2 calculated by GEM (a) and calcite mole change and aqueous concentration changes calculated by GEM (b)
표 Fig. 3-7-7. Variation of pH and calcite production on reaction temperature. The lines means pH value and the dotted line is the formed calcite according to the reaction temperature.
표 Fig. 3-8-1. Example of PHREEQC input for dissolution kinetics of a mineral
표 Fig. 3-8-2. Simulated pressure in the reaction vessel with temperature
표 Fig. 3-8-3. Simulated pH in the reaction vessel with temperature
표 Fig. 3-8-4. Simulated Mg (left) and NH4 and NH3 (g) concentration (right
표 Fig. 3-8-5. Simulated pH (left) and mineral concentration change (right).
표 Fig. 3-8-6. Simulated Mg (left) and NH4+ and NH3 (g) concentration (right).
표 Simulated pH (left) and mineral concentration change (right).
표 Fig. 3-9-1. Conceptual comparison of (geological) map with patent map
표 Fig. 3-9-2. Process for patent map and its application
표 Fig. 3-9-3. Trend of patent application in U.S.. Bar graphs represent the number of patents, and line graphs in represent the patents by Korean assignees.
표 Fig. 3-9-4. Number of patent application by assignees’ nationalities.
표 Fig. 3-9-5. Trend of patent application by assignees’ nationalities.
표 Fig. 3-9-6. Level of patents by the nationalities
표 Fig. 3-9-7. Size of family patent by assignees’ nationalities.
표 Fig. 3-9-8. Number of patents by highly ranked assignees
표 Fig. 3-9-9. Trend of patent application by assignees
표 Fig. 3-9-10. Level of patents by the assignees.
표 Fig. 3-9-11. Average size of family patent per number of patents (by assignees)
표 Fig. 3-10-1. S.Oneidensis MR-1의 pH 8 조건에서의 환원능력 실험. Fe(III)-citrate에 의해 적갈색 이던 배양액의 색이 S.Oneidensis MR-1의 환원 능력에 의해 환원되어 점차 밝아졌다
표 Fig. 3-10-2. NAu-1 과 S.Onediensis MR-1을 M1 medium에서 배양. T0부터 T4 까지 반응이 진행되었다. 각 반응군은 triplet으로 진행되었으며, 대조군으로는 no-bacteria 조건을 사용하였다.
표 Fig. 3-10-3. 2-35°에서 분석된 air-dried 시료의 XRD 패턴. 각 분석 시간별 반응군과 대조군을 함께 분석하였다.
표 Fig. 3-10-4. Ethylene glycol 및 Li-saturation/ethylene glycol 처리후 XRD pattern. 붉은 화살표는 10-Å 영역에서 나타나는 illitization의 transient phase의 흔적인 broad shoulder를 표시한 것이다.
표 Fig. 3-10-5. 1,10-phenanthroline assay를 통해 계산한 NAu-1의 환원 정도
표 Fig. 3-10-6. S.Onediensis MR-1에 의해 상등액으로 용출된 NAu-1의 구성 원소에 대한 ICP-AES 분석 결과
표 Fig. 3-10-7. T0 (A) 와 T4 (B) 에서 각각 분석한 SEM 이미지와 EDS spectrum (inset)
표 Fig. 3-10-8. TEM-EDS 분석을 통해 확인한 새로 형성된 illite
표 Fig. 3-10-9. SEM-EDS 분석을 통해 확인한 생물기원 탄산염 광물의 화학조성
표 Fig. 3-10-10. LaDuke 지역 탄산염 광물의 결정 방향에 따른 SAED pattern. a) [010]; b) [001]; c) [481] 에 대한 SAED pattern과 각 이미지의 inset line에 대한 line profile (d,e,f)을 확인하였다. Line profile에서 화살표로 표시된 부분들은 SAED pattern에 나타난 extra reflection 들이다.
표 Fig. 3-10-11. 미생물의 대사과정을 활용한 슬러그의 유용 금속 (Ca, Mg, Fe 등) 용출 실험 및 2차광물 형성 단계에서의 탄산염 광물 형성 pilot 실험을 위한 모식도
표 Fig. 3-11-1. Schematic diagram of the mineral carbonation test.
표 Fig. 3-11-2. Na and Al extraction efficiencies of red mud as a function of a solid dosage.
표 Fig. 3-11-3. Final pH of slate slurry as a function of the amount of red mud added.
표 Fig. 3-11-4. SEM images of (a) unreacted slate and (b) reacted slate with 1 M ammonium acetate solution
표 Fig. 3-11-5. Temporal pH variation of slate and red mud mixture during CO2 injection (40ml/min).
표 Fig. 3-11-6. CaCO3 contents of slate and red mud mixtures before and after carbonation tests.
표 Fig. 3-11-7. SEM images of unreacted slate, red mud, and slate and red mixture and reacted slate and red mud mixture.
표 Fig. 3-11-8. CaCO3 contents of slate and red mud mixtures before and after carbonation tests at different temperature conditions..
표 Fig. 3-11-9. SEM images of unreacted slate, red mud, and slate and red mixture and reacted slate and red mud mixture.
표 Fig. 3-11-10. Ca removal efficiencies for slate without red mud (25 oC wo/RM), slate slurry with red mud solid (25 oC S+S), slate leachate with red mud solid (25 oC L+S), and slate leachate with red mud solid (70 oC L+S).
표 Fig. 3-11-11. Carbonation efficiencies for slate without red mud (25 oC wo/RM), slate slurry with red mud solid (25 oC S+S), slate leachate with red mud solid (25 oC L+S), and slate leachate with red mud solid (70 oC L+S).

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