Analytical Science and Technology (분석과학)

The Korean Society of Analytical Sciences (한국분석과학회)
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Development of standard gas mixtures of hydrocarbons in methane contained in aluminum cylinders

알루미늄 실린더에서 혼합 탄화수소(C6-C10) 표준가스 개발

  • Kim, Yong-Doo (Center for Gas Analysis, Korea Research Institute of Standards and Scence (KRISS)) ;
  • Bae, Hyun-Kil (Center for Gas Analysis, Korea Research Institute of Standards and Scence (KRISS)) ;
  • Woo, Jin-Chun (Center for Gas Analysis, Korea Research Institute of Standards and Scence (KRISS)) ;
  • Lee, Sangil (Center for Gas Analysis, Korea Research Institute of Standards and Scence (KRISS)) ;
  • Oh, Sang-Hyub (Center for Gas Analysis, Korea Research Institute of Standards and Scence (KRISS)) ;
  • Lee, Jin Hong (Department of Environmental Engineering, Chungnam National University)
  • 김용두 (한국표준과학연구원 가스분석표준센터) ;
  • 배현길 (한국표준과학연구원 가스분석표준센터) ;
  • 우진춘 (한국표준과학연구원 가스분석표준센터) ;
  • 이상일 (한국표준과학연구원 가스분석표준센터) ;
  • 오상협 (한국표준과학연구원 가스분석표준센터) ;
  • 이진홍 (충남대학교)
  • Received : 2017.06.30
  • Accepted : 2017.09.13
  • Published : 2017.10.25
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Abstract

As the demand for natural gas increases with industrial development, the supply of natural gas is expected to become unstable with a shortage of imported natural gas. It is hence necessary to meet this demand by introducing and developing various types of natural gas, such as pipeline natural gas (PNG) and substituted natural gas (SNG), in addition to liquefied natural gas (LNG). The components included in PNG as well as their concentrations must be measured accurately, and a standard gas should be developed to accurately measure hydrocarbons ($C_6-C_{10}$), which are trace components included in natural gas. The components in the primary standard gas mixtures (PSMs) developed in the present study were hexane, heptane, octane, nonane, and decane with concentrations of $10-30{\mu}mol/mol$ with methane as the balance gas. Standard hydrocarbon ($C_6-C_{10}$) gas mixtures were prepared in aluminum cylinders by a gravimetric method with traceability following ISO 6142 with raw material gases, for which the purity of each component was analyzed completely. The prepared standard gas mixtures were analyzed by to evaluate the preparation consistency between the standard gas mixtures, the adsorbability of the cylinders, the variation of the stability, and the uncertainty. The results showed that aluminum cylinders have little adsorptive loss on their internal surfaces with excellent long-term stability. The developed standard gas mixture, containing hexane, heptane, octane, nonane, and decane with concentrations of $10-30{\mu}mol/mol$, showed an uncertainty in a range of 0.79 % - 1.63 %.

천연가스는 산업의 발전으로 인하여 수요가 계속 증가하고 있어 도입물량 부족 현상이 일어나 수급이 점차 불안정해질 것으로 예상된다. 액화천연가스 외에 파이프라인 천연가스 및 대체 천연가스등 다양한 형태의 가스 도입과 개발로 수요를 충당해야 할 필요성이 있다. 도입된 PNG의 성분과 농도를 정확하게 측정해야 한다. 이에 따른 천연가스 내에 있는 미량 성분인 탄화수소류($C_6-C_{10}$)의 정확한 측정이 요구되어 표준가스의 개발이 필수적이다. 이 연구에서 개발한 일차 표준물질에 대한 조성과 농도는 $10-30{\mu}mol/mol$의 헥산, 헵탄, 옥탄, 노난, 데칸이며 바탕가스는 메탄이다. 탄화수소류($C_6-C_{10}$)의 표준가스 제조는 각 성분 원료가스에 대한 순도분석이 완료된 가스를 ISO 6142에 근거하여 소급성이 있는 중량법으로 알루미늄 실린더에 제조하였다. 제조된 표준가스는 분석기로 표준가스간의 제조일치성, 실린더의 흡착성, 안정성 변화 및 불확도 평가를 하였다. 결과는 알루미늄 실린더에서 내부표면의 흡착 손실이 적고 장기 안정성이 매우 우수하다는 것을 알 수 있었고, 헥산, 헵탄, 옥탄, 노난, 데칸의 농도 $10-30{\mu}mol/mol$ 수준에서 불확도 0.79-1.63 %이내의 표준가스를 개발하였다.

Keywords

References

  1. K. J. Lee, J. Y. Her, S. M. Lee, S. J. Lee, Y. C. Ha, G. C. Ryu, C. Y. Lee, G. H. Kim and E. G. Yun, 'Stablishment of Measurement Standards for the Quality Assurance of PNG/SNG and Study on the Improvement Plan of Field Measurement Facilities, Korea Gas Corporation Report' 2013.
  2. G. E. Cirka and H. C. Soderberg, 'Dew Point Testing of Natural Gas, NOVA Corporation of Alberta', Ametek Technical Paper, 1990.
  3. Y. C. Ha and S. M. Lee, Korean Chem. Eng. Res., 49(1), 35-40 (2011). https://doi.org/10.9713/kcer.2011.49.1.035
  4. 'NGC, White Paper on Liquid Hydrocarbon Dropout in Natural Gas Infrastructure', NGC+ Gas Quality White Paper PL, 04-3-000 (2004).
  5. N. Bryant, J. Arizmendi, A. Kane, A. Laughton and A. Williams, 'Gas Quality Specification of PNG and Facility Adjustment', Advantica Report 7202 (2008).
  6. K. J. Lee, Y. C. Ha, J. Y. Her, J. C. Woo, Y. D. Kim and H. G. Bae, Korean Chem. Eng. Res., 53(4), 496-502 (2015). https://doi.org/10.9713/kcer.2015.53.4.496
  7. IS0 GUIDE 34, 'General requirements for the competence of reference material producers', 2000.
  8. ASTM D 1945-03, 'Analysis of Natural Gas by Gas Chromatography', 2001.
  9. ISO 6568, 'Natural gas-Simple analysis by gas chromatography', 1981.
  10. L. J. Papa et al., "Journal of Chromatographic Science", 10, 744-747 (1972). https://doi.org/10.1093/chromsci/10.12.744
  11. 'Establishment of national system on certified reference materials', KRISS/IR-2002-006, 1999.
  12. ISO 6142, 'Gas Analysis-Preparation of Calibration Gas Mixtures-Weighing Methods', 2015.
  13. M. J. T. Milton, G . M. Vargha and A. S. Brown, Metrologia, 48, R1-R9 (2011). https://doi.org/10.1088/0026-1394/48/5/R01
  14. N. Matsumoto, T. Watanabe, M. Maruyama, Y. Horimoto, T. Maeda and K. Kato, Metrologia, 41, 178-188 (2004). https://doi.org/10.1088/0026-1394/41/3/011
  15. ISO 6143, 'Gas Analysis-Comparison Methods for Determining and Checking the Composition of Calibration Gas Mixtures', 2001.
  16. ISO 6141, 'Gas analysis-Requirements for certificates for calibration gases and gas mixtures', 2000.
  17. I. Richard, Masel, 'Principles of Adsorption and Reaction on Solid Surfaces, Wiley-Interscience', 1996.
  18. G. C. Rhoderick, Analytical and Bioanalytical Chemistry, 383(1), 98-106 (2005). https://doi.org/10.1007/s00216-005-3381-3
  19. Kenji Kato, Takuro Watanabe, Hans-Joachim Heine, C. Boissiere, G. Schulz, J. C. Woo, J. S. Kim, S. H. Oh, H. G. Bae and Y. D. Kim, Metrlogia, 49, 08001 (2012). https://doi.org/10.1088/0026-1394/49/1A/08001
  20. M. J. T. Milton, F. Guenther, W. R. Miller and A. S. Brown, Metrologia, 43, L7- L10 (2006). https://doi.org/10.1088/0026-1394/43/3/N01
  21. ISO/IEC Guide 98-3 'Uncertainty of measurement, Guide to the expression of uncertainty in measurement', 2008.
  22. 'KRISS guide to the expression of uncertainty in measurement', KRISS-99-070-SP, 1999.
  23. ISO 6974-5, 'Natural gas-Determination of Composition with Defined Uncertainty by Gas Chromatography-Part 5,: Determination of Nitrogen, 24 Carbon dioxide and C1 to C5 and C6+ Hydrocarbons for a Laboratory and On-line Process Application using Three Columns', 2000.
  24. J. C. Woo, S. H. Oh, B. M. Kim, H. G. Bae, K. S. Kim and Y. D. Kim, Anal. Sci. Technol., 18(6), 475-482 (2005).
  25. M. H. Adriaan, van der Veen, Hima Chander, R. Paul Ziel1, Rob. M. Wessel1 Ed W. B, de Leer, Damian Smeulders, J. S. Kim, J. C. Woo, H. G. Bae and Y. D. Kim, Metrlogia, 47, 08019 (2006).
  26. 'Development and Dissemination of Reference Materials', KRISS/IR-2004-011, 2004.