Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Tuning Behavior of (Cyclic Amines + Methane) Clathrate Hydrates and Their Application to Gas Storage

고리형 아민이 포함된 메탄 하이드레이트의 튜닝과 가스 저장 연구

  • Ki Hun Park (Department of Integrated Energy and Infra System, Kangwon National University) ;
  • Dong Hyun Kim (Department of Integrated Energy and Infra System, Kangwon National University) ;
  • Minjun Cha (Department of Integrated Energy and Infra System, Kangwon National University)
  • 박기훈 (강원대학교 신산업개발 T-EMS 융합학과 에너지자원공학전공) ;
  • 김동현 (강원대학교 신산업개발 T-EMS 융합학과 에너지자원공학전공) ;
  • 차민준 (강원대학교 신산업개발 T-EMS 융합학과 에너지자원공학전공)
  • Received : 2023.03.13
  • Accepted : 2023.04.09
  • Published : 2023.08.01
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Abstract

In this study, the tuning phenomena, gas storage capacity, and thermal expansion behaviors of binary (cyclopentylamine + CH4) and (cyclopropylamine + CH4) clathrate hydrates were investigated for the potential applications of clathrate hydrates to gas storage. To understand the tuning behaviors of binary (cyclopentylamine + CH4) and (cyclopropylamine + CH4) clathrate hydrates, 13C solid-state NMR spectroscopy was used, and the results confirmed that maximum tuning factors for the binary (cyclopentylamine + CH4) and (cyclopropylamine + CH4) clathrate hydrates were achieved at 0.5 mol% and 1.0 mol% of guest concentration, respectively. The gas storage capacity of binary (cyclopentylamine + CH4) and (cyclopropylamine + CH4) clathrate hydrates were also checked, and the results showed the CH4 capacity of our hydrate systems was superior to that of binary (tetrahydrofuran + CH4) and (cyclopentane + CH4) clathrate hydrates. The synchrotron diffraction patterns of these hydrates collected at 100, 150, 200, and 250 K confirmed the formation of a cubic Fd-3m hydrate. In addition, the lattice constant of clathrate hydrates with cyclopentylamine and methane were larger than that with cyclopropylamine and methane due to the effects of molecular size and shape.

이 연구에서는 메탄 가스(CH4)와 함께 사이클로프로필아민(cyclopropylamine, CPrA)과 사이클로펜틸아민(cyclopentylamine, CPeA)을 이용한 하이드레이트의 튜닝효과, 가스 저장량, 그리고 하이드레이트의 열팽창 거동에 대해 논의하였다. 메탄 가스의 저장량을 극대화시킬 수 있도록 하이드레이트 튜닝 효과를 하이드레이트에 투입된 객체 분자의 농도를 달리 함에 따라 알아보았다. (CPrA+CH4) 하이드레이트의 경우, 0.5 mol% 정도의 농도에서 최대 튜닝효과가 발생하였으며, (CPeA+CH4) 하이드레이트는 기존 연구와 유사한 1.0 mol% 정도의 농도에서 최대 튜닝 효과가 발생하였다. (CPrA + CH4), (CPeA + CH4) 하이드레이트 모두 구조 II 하이드레이트를 형성한다고 알려진(테트라하이드로퓨란 + CH4), (사이클로펜탄 + CH4) 하이드레이트보다 더 많은 가스량을 저장하는 것으로 밝혀졌다. 100, 150, 200, 250 K의 조건에서(CPrA + CH4), (CPeA + CH4) 하이드레이트의 분말 X-선 회절 분석을 통해 각 온도별 격자 크기를 알아내고 그 차이를 분석하여 열팽창 거동을 분석하였다. 이에 따라, 객체 분자의 크기 차이로 인해(CPeA + CH4) 하이드레이트의 격자 상수가 더 큰 것으로 확인되었다.

Keywords

Acknowledgement

이 연구는 정부(과학기술정보통신부)의 재원으로 한국연구재단의 지원을 받아 수행된 연구(NRF-2021R1F1A1049420)이며, 이에 감사드립니다. 또한, 이 연구는 정부(산업통산자원부)의 재원으로 한국에너지기술평가원의 지원을 받아 수행된 연구(No. 20224000000080)이며, 이에 감사드립니다.

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