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Received March 18, 2007
Accepted May 5, 2007
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메탄/프로판 포접 하이드레이트 결정의 성장 특성
Morphology of Methane/Propane Clathrate Hydrate Crystal
한국생산기술연구원 차세대생산공정팀, 609-735 부산시 금정구 장전동 산30 1Department of Chemical and Biological Engineering University of British, 2216 Main Mall, Vancouver, British Columbia V6T 1Z4 2동국대학교 기계공학과, 100-715 서울시 중구 필동 3가
Advanced Manufacturing Technology team, Korea Institute of Industrial Technology, san 30, Jangjeon-dong, Geumjeong-gu, Busan 609-735, Korea 1University of British, Department of Chemical and Biological Engineering, 2216 Main Mall, Vancouver, British Columbia V6T 1Z4, Canada 2Department of Mechanical Engineering, Dongguk University, 3-ga, Pil-dong, Choong-gu, Seoul 100-715, Korea
songm@dgu.edu
Korean Chemical Engineering Research, August 2007, 45(4), 400-409(10), NONE Epub 28 August 2007
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Abstract
메탄/프로판 혼합기체의 포접 하이드레이트를 다양한 과냉 조건 하에서 생성시키며 결정의 성장 특성을 연구하였다. 먼저 내압 용기를 물과 고압의 혼합기체로 충진하고 충분히 교반하여 용액을 포화시킨 후, 내부 온도를 하이드레이트 생성온도 이하로 급격히 떨어뜨리고 이후에는 일정하게 유지하며 하이드레이트 결정의 핵생성, 이동, 성장 및 간섭을 현미경을 통하여 관찰하였다. 수행한 모든 실험조건에서 하이드레이트의 생성은 기체와 액체의 상경계면에서 막의 형태로 시작되었으며, 이후 용기 하부에서 생성된 다수의 소결정들이 부상하여 일부는 막의 밑면에 부착하고 일부는 하이드레이트 막으로부터 자라는 결정과 간섭하며 아래 방향으로 성장하였다. 막 근처에서 성장하는 결정들은, 비교적 작은 과냉 조건에서는 다면 기둥의 형태를 가지며 과냉이 커짐에 따라 형상이 수지상(dendrite)으로 천이하고 성장속도는 증가하며 가지간격은 감소하였다. 액체 영역 내부에서 관찰 된 부유 결정(floating crystals)들은 팔면체, 삼각판 및 육각 판 등 다양한 형태를 보이며, 과냉이 작을수록 팔면체 형태가 지배적이었다. 과냉이 커짐에 따라 부유 결정 역시 수지상으로 천이하며 성장하였다. 상세한 하이드레이트 결정의 성장 특성을 과냉과 기억효과(memory effect; 하이드레이트가 분해된 후에도 액체에 물분자의 입체 그물 결합구조가 잔존하는 현상)가 미치는 영향을 중심으로 기술하였다.
Morphology of methane/propane clathrate hydrate crystal was investigated under different undercooling conditions. After the water pressurized with compound guest gas was fully saturated by agitation, medium within the vessel was rapidly undercooled and maintained at the constant temperature while the visual observations using microscope revealed detailed features of subsequent crystal nucleation, migration, growth and interference occurring within liquid pool. The growth of hydrate was always initiated with film formations at the bounding surface between bulk gas and liquid regions under all tested experimental conditions. Then a number of small crystals ascended, some of which settled beneath the hydrate film. When undercooling was relatively small, some of the settled crystals slowly grew into faceted columns. As the undercooling increased, the downward growth of crystals underneath the hydrate film became dendritic and occurred with greater rate and with finer arm spacing. The shapes of the floating crystals within liquid pool were diverse and included octahedron and triangular or hexagonal platelet. When the undercooling was small, the octahedral crystals were found dominant. As the undercooling increased, the shape of the floating crystals also became dendritic. The detailed growth characteristics of floating crystals are reported focused on the influences caused by undercooling and memory effect.
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