보고서 정보
주관연구기관 |
경희대학교 산학협력단 Kyung Hee University |
보고서유형 | 1단계보고서 |
발행국가 | 대한민국 |
언어 |
한국어
|
발행년월 | 2014-07 |
과제시작연도 |
2013 |
주관부처 |
미래창조과학부 Ministry of Science, ICT and Future Planning |
등록번호 |
TRKO201400028227 |
과제고유번호 |
1345200846 |
사업명 |
기후변화대응기술개발 |
DB 구축일자 |
2014-11-22
|
키워드 |
이산화탄소.온실가스.알칸올아민.흡수제.저수계.비수계.재생에너지.Carbon dioxide.Greenhouse gas.Alkanolamine.Absorvent.Quasi-aqueous.Non-aqueous.Regeneration energy.
|
DOI |
https://doi.org/10.23000/TRKO201400028227 |
초록
▼
○ 재생에너지가 2.5 GJ/t-CO2, 흡수속도가 2.3 × 10-10 mol, CO2/cm2․s․Pa인 수계 흡수제와 흡수속도 ≥ 1.5 ×10-10, 반응열이 (kJ/mol-CO2) 60 kJ/mol-CO2)이하인 비수계 이산화탄소 흡수제 조성 확립
○ 이산화탄소 흡수 및 재생 메카니즘 규명
- NMR 및 X-ray 구조분석을 통하여 수계 및 비수계에서 일어나는 CO2
○ 재생에너지가 2.5 GJ/t-CO2, 흡수속도가 2.3 × 10-10 mol, CO2/cm2․s․Pa인 수계 흡수제와 흡수속도 ≥ 1.5 ×10-10, 반응열이 (kJ/mol-CO2) 60 kJ/mol-CO2)이하인 비수계 이산화탄소 흡수제 조성 확립
○ 이산화탄소 흡수 및 재생 메카니즘 규명
- NMR 및 X-ray 구조분석을 통하여 수계 및 비수계에서 일어나는 CO2 흡수 및 재생 메카니즘 규명
- 입체장애 및 치환체에 따른 이산화탄소 흡수 거동 변화 규명
- CO2 흡수종 구조 분석
○ 수계 흡수제 재생능 향상 방안 개발
- 재생 촉진제 및 흡수속도 증진제의 종류 및 역할에 대한 규명
- Cooperative interaction을 이용한 CO2 흡수능 향상가능성 확인
Abstract
▼
The chemical absorption of CO2 has been regarded as the most practical technology to capture CO2 from fossil fuel-fired power plants. On an industrial scale, aqueous solutions based on monoethanolamine (MEA) have been most frequently employed as CO2 capture solvents,
The chemical absorption of CO2 has been regarded as the most practical technology to capture CO2 from fossil fuel-fired power plants. On an industrial scale, aqueous solutions based on monoethanolamine (MEA) have been most frequently employed as CO2 capture solvents, due to the rapid CO2 absorption at low partial pressures. However, the chemical absorption process using aqueous solutions of MEA possesses a severe drawback in terms of regeneration energy. Upon interaction with CO2, MEA is known to produce thermally stable carbamate species, which is hard to desorb CO2 even at elevated temperature of 120 oC. As a means of reducing energy consumption during solvent regeneration, a sterically hindered amine like 2-amino-2-methyl-1-propanol (AMP) was introduced as an alternative to MEA.The presence of steric hindrance around the nitrogen atom of an alkanolamine was found to greatly reduce the stability of carbamate species, thereby leading to the formation of less thermally stable bicarbonate species.
Since the discovery of AMP, enormous effort has been devoted to understand the phenomenon observed during the absorption and desorption of CO2 in hindered amines. As a result, considerable amounts of kinetic, thermodynamic, and spectroscopic data have been accumulated on the CO2 absorption in hindered amines. However, the understanding of the nature of CO2 adducts involved is still primitive due to the lack of unambiguous evidences on the types of CO2 adducts formed during absorption and regeneration.
The X-ray structural evidence on the CO2 adducts generated during the CO2 absorption and desorption in an aqueous solution of a hinderedamine, t -butylaminoethanol (TBAE). From the structural analysis, we have found that CO2 interacts with TBAE in water in a 1:1 molar ratio at 40℃, exclusively forming a bicarbonate species, [TBAEH]HCO3. The bicarbonate species, [TBAEH]HCO3, is transformed in to a carbonate species, [TBAEH]2CO3, at regeneration condition of 80℃, which is more robust to desorb CO2 than [TBAEH]HCO3. In the early stage of the CO2 absorption, the formation of carbonate species ([TBAEH]2CO3) was predominant along with the generation of small amounts of zwitterionic species. With the progress of the absorption, the carbonate species was rapidly transformed into bicarbonate species ([TBAEH]HCO3),and the amounts of the zwitterionic species increased gradually. During desorption at elevated temperature in the absence of CO2, [TBAEH]HCO3 was found to transform into [TBAEH]2CO3, where CO32- strongly interacts with two [TBAEH]+via hydrogen bondings. This is a strong indication that the regeneration of a hindered alkanolamine from its CO2 adduct is not a simple reverse process of the absorption of CO2 in the hindered alkanolamine.
TBAPN and TAAPN exhibited the CO2 absorption capacities of about 1 mole CO2 per mole of amine, which are slightly higher than those of TBAE and TBAP. It is worthwhile to note that the desorption of CO2 from the CO2 adducts of TBAPN and TAAPN is much easier than that from the CO2 adducts of TBAE and TBAP. The desorption of CO2 from the CO2-loaded solutions of TBAPN and TAAPN was completed at 80℃, allowing the absorbents to be recycled without any loss of initial performance. As mentioned above, TBAE and TBAP were regenerated in less than 50% from their CO2 loaded solutions at the same desorption condition, suggesting that the functional group could affect the bonding mode of CO2 to a hindered amine.
Tetramethylammonium-based molten salts bearing a β-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate followed by hydrolysis and subsequent neutralization by using aqueous tetramethylammonium hydroxide. The CO2 capture performances of the TMAAs are evaluated and are shown to interact with CO2 in a 1:1 mode in both water and alcohol. FT-IR and 13C NMR spectroscopic studies on the interactions of TMAAs with CO2 indicate that the type of CO2 adduct varies with the solvent used. When water is used as the solvent, a bicarbonate species is produced, whereas hydroxyethylcarbonate and methylcarbonate species are generated in ethylene glycol and methanol, respectively. Computational calculations show that the carboxylate groups of TMAAs contribute towards the formation and stabilization of 1:1 CO2 adducts through hydrogen bonding interactions with the hydrogen atoms of the amino groups.
Tertiary alkanolamines including N-methyl-N,N-diethanolamine and
N ,N ,N -triethanolamine have been frequently employed as SO2 absorbents due to their considerably higher SO2 absorption capacities than physical solvents. However, there still remains one major obstacle in the use of tertiary alkanolamines as SO2 absorbents because they often tend to form thermally stable and irreversible SO2 adducts upon interaction with SO2.
Three different types of nitrile-functionalized amines, including 3-(N ,N -diethylamino)-propionitrile (DEAPN), 3-(N ,N -dibutylamino)propionitrile (DBAPN), and N -methyl-N,N -dipropionitrile amine (MADPN) were synthesized, and their SO2absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N ,N -diethyl-N -ethanol amine (DEEA), N ,N -dibutyl-N -ethanol amine (DBEA), and N -methyl-N,N -diethanol amine (MDEA). Absorption-desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO2 through oxygen atom, forming an ionic compound with a covalently bound -OSO2- group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO2 through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities.
목차 Contents
- 표지 ... 1
- 제출문 ... 2
- 보고서 요약서 ... 3
- 요약문 ... 4
- 목차 ... 8
- 표목차 ... 10
- 그림목차 ... 11
- Scheme 목차 ... 12
- SUMMARY ... 13
- CONTENTS ... 17
- 제1장 연구개발과제의 개요 ... 18
- 제1절 서론 ... 18
- 제2절 습식 화학 흡수 기술 ... 19
- 제2장 국내외 기술개발 현황 ... 32
- 제1절 국내기술 동향 및 수준 ... 32
- 제2절 국외기술 동향 및 수준 ... 33
- 제3장 연구개발수행 내용 및 결과 ... 46
- 제1절 아민계 및 이온성액체계 CO2 흡수제 ... 46
- 제2절 아민계 SO2 흡수제 ... 77
- 제4장 목표달성도 및 관련분야에의 기여도 ... 87
- 제5장 연구개발결과의 활용계획 ... 91
- 제1절 연구개발결과의 활용방안 ... 91
- 제2절 기대성과 ... 91
- 제6장 연구시설ㆍ장비 현황 ... 93
- 제7장 참고문헌 ... 94
- 끝페이지 ... 96
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