한국가스학회지 (Journal of the Korean Institute of Gas)

  • 제24권5호
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  • Pages.56-64
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  • 2020
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  • 1226-8402(pISSN)
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  • 2713-6922(eISSN)
한국가스학회 (The Korean Institute of GAS)
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해저 유동관내 하이드레이트 형성 방지를 위한 PVCap의 억제효과에 관한 실험 연구

Experimental Study on the Inhibition Effect of PVCap to Prevent Formation of Hydrate in Subsea Flowline

  • 김영민 (한국지질자원연구원 석유해저연구본부) ;
  • 최준호 (광성지엠(주) 기술연구소) ;
  • 이정환 (전남대학교 에너지자원공학과)
  • Kim, Young-Min (Petroleum&Marine Research Division, Korea Institute of Geoscience and Mineral Resources) ;
  • Choi, Jun-Ho (Institute of Technology, Gwang-Sung GM) ;
  • Lee, Jeong-Hwan (Dept. of Energy and Resources Engineering, Chonnam National University)
  • 투고 : 2020.07.29
  • 심사 : 2020.10.24
  • 발행 : 2020.10.31
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초록

해양 가스전의 다양한 생산환경에서 PVCap의 하이드레이트 억제 성능을 평가하고자 PVCap 농도, 과냉각 온도, 염수 농도, MEG 혼합 농도 변화에 따라 하이드레이트 지연시간을 측정하였다. 이를 위해 고압의 하이드레이트 반응 실험 장치를 제작하였으며, 하이드레이트 평형 조건 및 지연시간 측정결과를 선행 실험과 비교함으로써 실험장치의 신뢰성에 대한 타당성을 검증하였다. 과냉각 온도 6.1, 9.2, 12.1℃조건에서 PVCap 농도 0.1~1 wt%의 억제 성능을 분석한 결과, 과냉각 온도가 증가함에 따라 PVCap으로 인한 지연시간이 감소하였다. 염수 농도가 3 wt%에서 7 wt%까지 증가하였을 때, PVCap 폴리머 체인의 구조 저하가 발생하여 PVCap 0.5 wt% 조건에서 최대 78%까지 지연시간이 감소하였다. MEG 10 wt%와 PVCap을 혼합한 HHI(hybrid hydrate inhibitor)의 경우, 아억제(under-inhibition) 영향으로 PVCap 1 wt%에 비해 지연시간의 변화가 크지 않았으나, MEG 20 wt%인 HHI에서는 하이드레이트 억제 효율이 1.7배 증가하였다.

This study presents the hydrate induction time of PVCap according to subcooling temperature, salt concentration, and MEG concentration in order to analyze the inhibition effect of PVCap in various production environments of offshore gas fields. A high-pressure hydrate generator was made for the hydrate formation experiments. It was verified that the apparatus had sufficient reliability by comparing the results of hydrate equilibrium conditions and induction time from the apparatus with published reference data. As the subcooling temperature increased from 6.1℃ to 12.1℃, the induction time of PVCap concentration of 0.1~1 wt% decreased. When the salt concentration increased from 3 wt% to 7 wt%, the induction time was reduced by up to 78% under the condition of 0.5 wt% PVCap due to polymer structure degradation by salt effect. In the case of HHI (hybrid hydrate inhibitor) made by mixing MEG 10 wt% and PVCap, the change in induction time was not large compared to PVCap 1 wt% due to the under-inhibition effect. On the other hand, the hydrate inhibition efficiency of HHI with MEG 20wt% increased 1.7 times compared to PVCap.

키워드

참고문헌

  1. Carroll, J., Natural Gas Hydrates A Guide For Engineers, Gulf Professional Publishing, Elsevier, USA, 17-23, (2014)
  2. Kim, J., Chang, D., Chang, K., and Noh, Y. "Determination of Hydrate Injection Rate for Flowline Based on Monte Carlo Method", Journal of Loss Prevention in the Process Industries, 44, 62-72, (2016) https://doi.org/10.1016/j.jlp.2016.08.012
  3. Kim, J., Seo, Y., Kang, S.P., Kim, H., Sohn, Y.H., and Chang, D. "Prevention of Methane Hydrate Re-formation in Transport Pipeline Using Thermodynamic and Kinetic Hydrate Inhibitors", Journal of Petroleum Science and Engineering, 154, 114-125, (2017) https://doi.org/10.1016/j.petrol.2017.04.011
  4. Park, J., Kim, H., Sheng, Q., Wood, C. D., and Seo, Y. "Kinetic Hydrate Inhibition Performance of Poly (vinyl caprolactam) Modified with Corrosion Inhibitor Groups", Energy & Fuels, 31(9), 9363-9373, (2017) https://doi.org/10.1021/acs.energyfuels.7b01956
  5. Sloan, E.D., and Koh, C.A. Clathrate Hydrates of Natural Gases, 3rd ed., CRC Press, Florida, (2008)
  6. Sum, A.K. "Prevention, Management, and Remediation Approaches for Gas Hydrates in the Flow Assurance of Oil/Gas Flowlines", Offshore Technology Conference, (2013)
  7. Makogon, T.Y., Larsen, R., Knight, C., and Sloan Jr., E.D. "Melt Growth of Tetrahydrofuran Clathrate Hydrate and its Inhibition: Method and First Results", Journal of Crystal Growth, 179, 258-262, (1997) https://doi.org/10.1016/S0022-0248(97)00118-8
  8. Kim, H.T, Kim, E.S., Kim, K.S., and Kang, S.P. "Smart Ionic Liquids for Hydrate Inhibition", Journal of Korean Industrial Chemistry News, 16(1), 33-41, (2013)
  9. Chin, Y.D., and Srivastava, A. "Advances in LDHIs and Applications", Offshore Technology Conference, 1-19, (2018)
  10. Park, H. "Inhibition Effect of Natural Clays, Water Soluble Polymers, and Ionic Liquids on Methane Hydrate Formation", Ph.D Dissertation, Kyungpook National University, (2016)
  11. Sloan, E.D., Subramanian, S., Matthews, P.N., Lederhos, J.P., and Khokhar, A.A. "Quantifying Hydrate Formation and Kinetic Inhibition", Journal of American Chemical Society, 37(8), 3124-3132, (1998)
  12. Huff, T., Cook, S., Trebing, R., Glover, M., Garza, T., and Thieu, V. "Simple and Cost-effective Hydrate Prevention for Flowback After Hyraulic Fracturing: Kinetic Hydrate Inhibitor (KHI)/Methanol Mixture", SPE Annual Technical Conference and Exhibition, 1-6, (2013)
  13. Kim, J.K., Shin, K.C., Cho, S.J., Lee, J.D, and Seo, Y.T. "Synergistic Hydrate Inhibition of Monoethylene Glycol with Poly(vinylcaprolactam) in Thermodunamically Underinhibited System", Journal of Physical Chemistry B, 118(30), 9065-9075, (2014) https://doi.org/10.1021/jp503435t
  14. Wang, F., Luo, S.J., Fu, S.F., Jia, Z.Z., Dai, M., Wang, C.S, and Guo, R.B. "Methane hydrate formation with surfactants fixed on the surface of polystyrene nanospheres", Journal of Materials Chemistry A, 3, 8316-8323, (2015) https://doi.org/10.1039/C5TA01101A
  15. Sloan, E.D. Clathrate Hydrates of Natural Gases, 2nd ed., CRC Press, Florida, (1998)
  16. Perfeldt, C. M., Sharifi, H., von Solms, N., and Englezos, P. "Oil and Gas Pipelines with Hydrophobic Surfaces Better Equipped to Deal with Gas Hydrate Flow Assurance Issues", Journal of Natural Gas Science and Engineering, 27, 852-861, (2015) https://doi.org/10.1016/j.jngse.2015.09.044
  17. Rasoolzadeh, A., Javanmardi, J., and Ansaripoor, G. "Experimental Study of Methane Hydrate Formation and Dissociation in the Presence of PVP and BMIM-BF4", International Chemical Engineering Congress and Exhibition, 1-4, (2014)
  18. Meindinyo, R.E.T., and Svartaas, T.M. "Gas Hydrate Growth Kinetics: A Parametric Study", Energies, 9(12), 1-29, (2016)
  19. Hemmingsen, P.V., Li, X., and Kinnari, K. "Hydrate Plugging Potential in Underinhibited Systems", International Conference on Gas Hydrate, 1-12, (2008)