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天然气中硫化氢含量及硫同位素联测方法

杨华敏 王萍 陶成 王杰 马亮帮

杨华敏, 王萍, 陶成, 王杰, 马亮帮. 天然气中硫化氢含量及硫同位素联测方法[J]. 石油实验地质, 2024, 46(1): 166-172. doi: 10.11781/sysydz202401166
引用本文: 杨华敏, 王萍, 陶成, 王杰, 马亮帮. 天然气中硫化氢含量及硫同位素联测方法[J]. 石油实验地质, 2024, 46(1): 166-172. doi: 10.11781/sysydz202401166
YANG Huamin, WANG Ping, TAO Cheng, WANG Jie, MA Liangbang. Combined measurement of hydrogen sulfide content and sulfur isotope in natural gas[J]. PETROLEUM GEOLOGY & EXPERIMENT, 2024, 46(1): 166-172. doi: 10.11781/sysydz202401166
Citation: YANG Huamin, WANG Ping, TAO Cheng, WANG Jie, MA Liangbang. Combined measurement of hydrogen sulfide content and sulfur isotope in natural gas[J]. PETROLEUM GEOLOGY & EXPERIMENT, 2024, 46(1): 166-172. doi: 10.11781/sysydz202401166

天然气中硫化氢含量及硫同位素联测方法

doi: 10.11781/sysydz202401166
基金项目: 

国家自然科学基金面上项目 42273015

中国石化油田部先导项目 YTBXD-FCZY-2023-1-07-003

详细信息
    作者简介:

    杨华敏(1979-), 女, 高级工程师, 从事同位素地球化学分析技术研究。E-mail: yanghm7984@163.com

  • 中图分类号: TE135

Combined measurement of hydrogen sulfide content and sulfur isotope in natural gas

  • 摘要: 我国含硫化氢天然气勘探潜力巨大,硫化氢成因、来源、形成机制为石油工作者所关注。硫化氢含量及硫同位素是两项常用且重要的判识指标。因硫化氢的强毒性,国内很多实验室较少检测或取消了此类检测项目。通过前处理流程优选硫化氢转化试剂,同时通过改进同位素质谱仪配套设备——调试硫同位素法拉第杯离子束聚焦等参数,安装特制色谱柱、特氟龙管路、硫反应管等,搭建了硫化氢含量及硫同位素联测技术平台;其次将高纯二氧化硫标准气替换为低浓度、低压力、小体积的工作标准气,通过系统条件实验探索(稳定性,标样分析等),确定最优实验条件;最后将反应生成的固体沉淀物送入质谱仪中进行硫同位素组成信息的检测,通过与标准纯含硫物质同位素组成的信号对比,计算出待测气体中硫化氢含量。用该方法对鄂尔多斯盆地大牛地气田、富县气田、鄂西渝东红星地区部分含硫化氢天然气进行硫化氢含量和硫同位素测试,所测结果稳定、精度良好,同时与外部实验室比对结果吻合。与传统方法比,该方法一次进样可得到硫含量和硫同位素数值;优选醋酸银试剂一步化学法一次性转化,减少同位素分馏;另一方面将硫化氢转化为固态硫化银,与标准物质硫化银硫同位素直接对比,同位素溯源结果更具可靠性;以低浓度、低压力、小体积的二氧化硫作为工作标准气,降低了实验室安全风险和仪器损害,满足环保安全需求。

     

  • 图  1  含硫化氢天然气样品单次分析硫化氢含量和硫同位素图谱

    Figure  1.  Chromatogram of hydrogen sulfide content and sulfur isotope by single analysis of samples of natural gas containing hydrogen sulfide

    表  1  实验室内配制硫化氢标准气含量测定结果

    Table  1.   Measurement results of hydrogen sulfide standard gas prepared in laboratory

    样品名称 测定次数 总反应体积/ L 总沉淀量/ mg H2S体积浓度/ 10-6 测定平均值/ 10-6 推荐值/ 10-6
    标气 1 74.95 4.51 5.44 5.38 5.58
    标气 2 68.45 4.02 5.31 5.38 5.58
    下载: 导出CSV

    表  2  标准物质的硫同位素测定结果

    Table  2.   Measurement results of sulfur isotope of standard substance

    样品名称 测定次数 δ34SVCDT测定值/‰ 推荐值/‰ 平均值/‰ 标准偏差/‰
    GBW04414 1 -0.03 -0.07 -0.02 0.11
    2 -0.18
    3 0.11
    4 -0.01
    5 0.02
    GBW04415 1 22.06 22.15 22.10 0.14
    2 21.93
    3 22.32
    4 22.07
    5 22.11
    IAEA (C6H8O2N2S) 1 5.91 5.91 0.04
    2 5.96
    3 5.92
    4 5.91
    5 5.84
    下载: 导出CSV

    表  3  含硫化氢天然气样品中硫化氢含量和硫同位素测试结果

    Table  3.   Measurement results of hydrogen sulfide content and sulfur isotope in samples of natural gas containing hydrogen sulfide

    样品井号 层位 测定次数 总反应体积/mL 总沉淀量/ mg H2S质量含量/ (mg/m3) H2S体积浓度 δ34SVCDT
    测定值/ 10-6 平均值/ 10-6 相对偏差/ % 测定值/ ‰ 平均值/ ‰ 相对偏差/ %
    PG19 M5-5 1 110 4.60 5 738 3 780 3 789 0.45 29.87 29.80 0.29
    2 258 10.87 5 781 3 809 29.82
    3 250 10.45 5 735 3 778 29.7
    XF11 M5-1 1 384 5.96 2 130 1 403 1 373 7.65 20.5 20.45 0.30
    2 490 7.91 2 215 1 459 20.38
    3 169 2.35 1 907 1 256 20.46
    D1-544 M5-7 1 141 3.12 3 036 2 000 2 025 1.75 26.75 26.74 0.05
    2 265 6.01 3 112 2 050 26.73
    3 71 1.34 2 590 1 706 - - 27.18 - -
    HY1 吴二段 1 193 3.04 2 161 1 424 1 465 3.91 12.08 12.01 0.88
    2 397 6.61 2 284 1 505 11.93
    3 105 0.95 1 241 818 - - 12.28 - -
    注:表中“-”表示该次实验所得沉淀量少,结果误差较大,不做统计分析。
    下载: 导出CSV

    表  4  天然气样品中硫化氢含量和硫同位素测试结果比对

    Table  4.   Comparison testing results of hydrogen sulfide content and sulfur isotope in natural gas samples

    样品井号 H2S体积浓度 δ34SVCDT
    本方法/10-6 海洋三所/10-6 相对偏差/% 本方法/‰ 海洋三所/‰ 相对偏差/%
    PG19 3 789 3 645 3.87 29.80 29.51 0.97
    D1-544 2 025 2 134 5.24 26.74 26.30 1.66
    下载: 导出CSV
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  • 收稿日期:  2023-05-19
  • 修回日期:  2023-12-13
  • 刊出日期:  2024-01-28

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