天然气中氦含量测定方法对比及意义

    The comparison of the measurement methods of the helium content in natural gas and its implication

    • 摘要: 氦气是重要的稀缺性战略资源,在众多高新技术及民生领域发挥着不可替代的作用。准确测量天然气中氦气含量对正确认识氦气资源品位、科学评价氦气资源规模具有重要意义。目前,实验室内进行天然气中氦含量测定普遍采用气相色谱法和稀有气体同位素质谱法,但针对这两种方法的准确性和差异性探讨比较少,认识也相对薄弱,给分析样品的选送及数据的使用带来不少困惑。本文通过对天然气中氦含量不同测定方法的分析,对比了同位素质谱法和气相色谱法测试结果差异及相关性,提出了根据色谱法测试结果进行校正的方法。研究结果表明,质谱法在准确性、重复性等方面优于色谱法,而色谱法则操作方法简单、经济快捷,便于样品的批量分析。尽管受前处理和实验条件及流程等方面差异影响,不同实验室的四极杆质谱仪测试结果存在一定差异,但其差异小于同一单位不同时期色谱法测试结果的差异,表明质谱法本身精度更高、结果更为可靠。对塔里木盆地顺北、和田河等油气田常规天然气和四川盆地威远气田页岩气均同时采用两种方法进行氦气含量测定,开展相关性研究,结果表明所有样品质谱法(y%)和色谱法所测得He含量(x%)之间呈良好的线性相关(y=1.135 4x+0.005 7,R2=0.992 9)。这为色谱法测试所得He含量的科学和准确校正提供了新的思路和方法,大大节约了时间成本和经济成本,具有广阔的推广空间。

       

      Abstract: Helium is an important scarce resource with strategic value, and it plays an irreplaceable role in numerous high-tech and people’s livelihood fields. The accurate measurement of the helium content in natural gas has crucial implication for the correct understanding of the helium resource abundance and scientific evaluation of helium resource scale. The gas chromatography and noble gas isotopic mass spectrometry are commonly used to measure the helium content in natural gas in the laboratory, however, the discussions and understandings on the accuracy and difference of these two methods are weak, which has caused many confusions regarding the sample presentation and the use of data. This work intends to compare the difference and correlation of analytic results of gas chromatography and isotopic mass spectrometry based on the measurements of helium contents in natural gas, and further propose the correction method for the analytical results of gas chromatography. The study indicates that, the mass spectrometry is superior to gas chromatography in terms of accuracy and repeatability, whereas the gas chromatography is economical and fast with simple operation, which is convenient for batch analysis of samples. As affected by the differences on the pretreatment, experimental conditions and procedures, the results measured by the same type of quadrupole mass spectrometry in different laboratories display some differences, which are less than those of the results measured by the gas chromatography in the same laboratory at different times. This suggests that the mass spectrometry has higher accuracy and more reliable results. The helium contents in conventional gas from the oil and gas fields such as Shunbei and Hetianhe in the Tarim Basin and shale gas from Weiyuan gas field in the Sichuan Basin have been measured by both mass spectrometry(y%) and gas chromatography(x%) accompanied with the correlation analysis, and the results display favorable linear correlation(y=1.135 4x+0.005 7, R2=0.992 9). This provides new ideas and methods for the scientific and accurate correction of the helium content obtained by gas chromatographic method, and it greatly saves time and economic costs with broad promotion space.

       

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