Geochemical characteristics of light hydrocarbons in Upper Paleozoic tight gas from Daniudi Gas Field, Ordos Basin
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摘要: 大牛地气田是鄂尔多斯盆地典型致密砂岩大气田之一。为了更深入了解该区天然气的成因和来源，揭示天然气运移相态，对大牛地气田上古生界致密气开展了轻烃地球化学特征分析。研究表明，该区上古生界致密气C5-7轻烃组成具有异构烷烃优势分布，C6-7轻烃组成中芳烃含量整体偏低(＜10%)，甚至未检出芳烃，C7轻烃组成具有甲基环己烷优势分布特征，甲基环己烷相对含量均超过50%。上二叠统下石盒子组天然气K1值、K2值均与二叠系山西组和石炭系太原组天然气一致，而δ13C1值则与山西组天然气一致，与太原组天然气有明显不同。与山西组天然气相比，下石盒子组天然气整体具有偏低的苯/正己烷、苯/环己烷和甲苯/正庚烷比值，以及明显偏高的正庚烷/甲基环己烷比值。轻烃地球化学特征及烷烃气碳氢同位素组成综合表明，大牛地气田上古生界天然气为典型煤成气，其中山西组和太原组天然气均为原地自生自储，而下石盒子组天然气为下伏山西组烃源岩生成的天然气经历了游离相垂向运移聚集形成，太原组烃源岩不具有显著贡献。受天然气运移和水溶等作用影响，庚烷值、异庚烷值、苯/正己烷比值等轻烃指标直接用于判识大牛地气田致密气成熟度会存在偏差。Abstract: The Daniudi Gas Field is one of the typical tight sandstone gas fields in the Ordos Basin. In order to better understand the genetic types and source of natural gas and reveal the migration phase of natural gas, the geochemical analysis of light hydrocarbons in the Upper Paleozoic tight gas from the Daniudi Gas Field has been conducted in this study. The results indicate that, the C5-7 light hydrocarbons in the Upper Paleozoic tight gas are dominated by iso-alkanes, and the C6-7 light hydrocarbons display low contents of aromatics (< 10%), which are even undetectable. The C7 light hydrocarbons are dominated by methylcyclohexane (MCH) with the relative MCH contents exceeding 50%. The K1 and K2 values of natural gas from the Lower Shihezi Formation (P1x) are consistent with those from the Shanxi (P1s) and Taiyuan (C3t) formations, respectively. The δ13C1 values of the P1x gas are consistent with those of the P1s gas and significantly different from those of the C3t gas. Compared with the P1s gas, the P1x gas mainly displays lower benzene/n-hexane, benzene/cyclohexane and toluene/n-heptane ratios, as well as significantly higher n-heptane/methylcyclohexane ratios. Geochemical characteristics of light hydrocarbons and carbon and hydrogen isotopic compositions of alkanes indicate that, the Upper Paleozoic natural gas from the Daniudi Gas Field is typical coal-derived gas. The P1s and C3t gases were in-situ self-generated and self-accumulated, whereas the P1x gas was mainly derived from the underlying P1s source rocks and accumulated via vertical migration in free phase, with insignificant contributions of the C3t source rocks. Due to the effect of migration and water solution of natural gas, the deviation exists in the identification of thermal maturity for tight gas from the Daniudi Gas Field using the light hydrocarbon indexes such as heptane and isoheptane values and benzene/n-hexane ratios.
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图 1 鄂尔多斯盆地大牛地气田位置(a)及地层综合柱状图(b)
据参考文献[24]修改。
Figure 1. Location of Daniudi Gas Field in Ordos Basin (a) and stratigraphic column (b)
图 2 大牛地气田上古生界天然气轻烃色谱图
1.2-甲基戊烷；2.3-甲基戊烷；3.正己烷；4.甲基环戊烷；5.苯；6.环己烷；7.2-甲基己烷；8.3-甲基己烷；9.正庚烷；10.甲基环己烷。
Figure 2. Chromatogram of light hydrocarbons in natural gas from Upper Paleozoic, Daniudi Gas Field
图 3 大牛地气田上古生界天然气C5-7正构烷烃、异构烷烃和环烷烃组成
底图据戴金星等[27]。
Figure 3. Ternary diagram of n-C5-7, iso-C5-7 and cyc-C5-7 in natural gas from Upper Paleozoic, Daniudi Gas Field
图 4 大牛地气田上古生界天然气正庚烷、甲基环己烷和二甲基环戊烷相对组成
底图据戴金星等[27]。
Figure 4. Ternary diagram of n-heptane, methylcyclohexane and various dimethylcyclopentane in natural gas from Upper Paleozoic, Daniudi Gas Field
图 5 大牛地气田上古生界天然气δD1与δ13C1值相关图
底图据参考文献[28]。
Figure 5. Correlation between δD1 and δ13C1 values of natural gas from Upper Paleozoic, Daniudi Gas Field
图 6 大牛地气田上古生界天然气庚烷值和异庚烷值相关图
底图据THOMPSON[18]。
Figure 6. Correlation between heptane and isoheptane values of natural gas from Upper Paleozoic, Daniudi Gas Field
图 7 大牛地气田上古生界天然气苯/正己烷(a)、甲苯/正庚烷(b)比值与δ13C1值相关图
Figure 7. Correlation between benzene/n-hexane (a), toluene/n-heptane (b) and δ13C1 values of natural gas from Upper Paleozoic, Daniudi Gas Field
图 8 大牛地气田上古生界天然气(2-MH+2, 3-DMP)/C7与(3-MH+2, 4-DMP)/C7相关图
Figure 8. Correlation between (2-MH+2, 3-DMP)/C7 and (3-MH+2, 4-DMP)/C7 of natural gas from Upper Paleozoic, Daniudi Gas Field
图 9 大牛地气田上古生界天然气(P2+N2)/C7与P3/C7相关图
Figure 9. Correlation between (P2+N2)/C7 and P3/C7 of natural gas from Upper Paleozoic, Daniudi Gas Field
图 10 大牛地气田上古生界天然气δ13C1(a)和δ13C2(b)与正庚烷/甲基环己烷相关图
Figure 10. Correlation between δ13C1 (a), δ13C2 (b) and n-heptane/methyl-cyclohexane of natural gas from Upper Paleozoic, Daniudi Gas Field
图 11 大牛地气田下石盒子组(P1x)天然气苯/正己烷(a)和正庚烷/甲基环己烷比值(b)分布
Figure 11. Distribution of benzene/n-hexane (a) and n-heptane/methylcyclohexane (b) ratios of Lower Shihezi natural gas from Daniudi Gas Field
图 12 大牛地气田上古生界天然气苯/正己烷与苯/环己烷(a)、甲苯/正庚烷(b)相关图
Figure 12. Correlation between benzene/cyclohexane (a), toluene/n-heptane (b) and benzene/n-hexane of Upper Paleozoic natural gas from Daniudi Gas Field
表 1 大牛地气田上古生界天然气轻烃相对组成和烷烃气碳氢同位素值
Table 1. Relative composition of light hydrocarbons and carbon and hydrogen isotopic values of alkanes in natural gas from Upper Paleozoic, Daniudi Gas Field
井号 深度/m 层位 C5-7相对组成/% C6-7相对组成/% C7相对组成/% 甲基环己烷指数/% δ13CV-PDB /‰ δD1 V-SMOW / ‰ 正构烷烃 异构烷烃 环烷烃 链烷烃 环烷烃 芳烃 二甲基环戊烷 正庚烷 甲基环己烷 CH4 C2H6 D1 P1x 23.8 49.8 26.4 52.0 47.2 0.8 24.4 12.9 62.7 61.3 -37.4 -25.7 -201 D2 2 548 P1x 24.2 50.9 24.8 62.0 36.8 1.3 21.0 22.8 56.2 55.2 -35.8 -26.1 -181 D3 2 633 P1x 22.4 51.1 26.5 52.4 46.0 1.6 25.8 11.5 62.8 61.4 -37.7 -25.2 -197 D4 2 675 P1x 28.6 54.1 17.3 77.0 22.5 0.5 19.3 38.3 42.4 41.9 -35.8 -26.2 -181 D5 2 709 P1x 34.8 44.5 20.7 70.5 28.9 0.6 18.9 39.1 42.0 41.4 -35.5 -26.5 -185 D6 2 716 P1x 23.8 48.3 27.9 58.8 40.6 0.6 36.7 18.3 45.0 44.4 -37.1 -25.9 -197 D7 2 749 P1x 29.9 43.9 26.2 62.9 36.3 0.7 17.2 32.0 50.8 50.0 -34.3 -25.9 -181 D8 2 789 P1x 23.6 54.8 21.6 59.8 39.8 0.4 29.2 14.5 56.3 55.2 -34.7 -25.4 -189 D9 2 660 P1x 31.0 44.1 24.9 65.7 34.3 - 16.0 32.4 51.6 50.9 -35.7 -26.0 -184 D10 2 631 P1x 22.6 53.3 24.1 54.9 44.7 0.4 28.2 10.4 61.4 60.2 -37.2 -24.9 -198 D11 2 667 P1x 22.8 48.5 28.7 58.7 40.3 1.0 16.4 24.0 59.5 58.6 -34.5 -25.8 -181 D12 2 669 P1x 34.5 43.7 21.8 70.1 29.7 0.2 13.7 38.3 48.0 47.3 -35.4 -25.7 -182 D13 2 673 P1x 19.6 52.1 28.2 55.9 44.0 0.1 20.9 11.4 67.7 66.6 -34.6 -25.2 -183 D14 2 698 P1x 34.4 47.5 18.1 75.6 24.4 - 25.6 37.7 36.7 36.4 -35.5 -26.2 -188 D15 2 703 P1x 20.9 52.4 26.7 57.7 42.3 - 20.8 15.0 64.3 63.3 -34.9 -25.6 -180 D16 2 700 P1x 28.3 51.2 20.5 72.1 27.9 - 14.9 38.0 47.0 46.6 -35.5 -25.7 -182 D17 2 635 P1x 25.5 54.8 19.7 63.8 36.2 - 29.4 15.0 55.6 54.6 -36.6 -26.0 -197 D18 2 716 P1x 21.1 51.3 27.5 57.4 42.6 - 20.8 14.8 64.4 63.5 -35.0 -25.6 -181 D19 2 675 P1x 24.6 52.1 23.3 65.1 34.9 - 16.8 25.7 57.5 56.8 -35.0 -26.2 -180 D20 2 685 P1x 25.8 48.7 25.5 63.9 36.1 - 17.2 28.4 54.4 53.9 -35.2 -25.8 -181 D21 2 680 P1x 22.8 51.5 25.7 61.0 39.0 - 17.6 21.9 60.5 59.8 -35.1 -26.0 -179 D22 2 630 P1s 24.5 53.7 21.8 60.3 38.8 0.8 26.2 17.1 56.7 55.6 -36.0 -25.1 -197 D23 2 830 P1s 24.1 52.5 23.4 58.5 39.7 1.8 26.5 17.2 56.4 55.3 -36.0 -25.3 -195 D24 2 783 P1s 21.6 47.0 31.4 44.4 47.5 8.1 20.2 11.2 68.6 67.2 -35.0 -24.0 -196 D25 2 831 P1s 22.9 52.0 25.1 57.3 41.4 1.3 28.5 14.7 56.9 55.9 -35.9 -24.6 -193 D26 2 819 P1s 25.1 51.6 23.3 58.1 41.2 0.7 20.5 17.4 62.1 60.7 -33.3 -24.8 -179 D27 2 812 P1s 23.3 49.1 27.6 53.4 44.0 2.6 22.1 14.7 63.1 61.9 -34.1 -24.8 -186 D28 2 846 P1s 21.5 46.2 32.3 55.8 41.6 2.6 31.5 17.1 51.4 50.6 -35.8 -24.5 -193 D29 2 744 P1s 19.7 49.6 30.7 49.0 49.3 1.7 20.4 9.2 70.4 69.1 -33.8 -23.9 -192 D30 2 879 P1s 22.1 53.5 24.4 56.2 43.8 - 22.0 11.0 67.0 65.9 -34.5 -25.1 -186 D31 2 881 P1s 32.5 50.8 16.7 62.4 35.9 1.7 35.3 14.0 50.7 50.1 -37.0 -25.0 -209 D32 2 826 P1s 22.5 51.8 25.8 55.5 44.5 - 21.1 12.0 66.8 65.6 -34.4 -25.5 -187 D33 P1s 28.4 45.3 26.3 49.3 50.3 0.5 20.1 15.0 64.8 63.6 -36.9 -25.0 -201 D34 2 820 P1s 24.6 54.5 20.9 56.4 42.9 0.7 24.8 12.9 62.4 61.3 -36.2 -24.2 -201 D35 2 795 C3t 25.8 49.9 24.3 57.0 39.9 3.1 20.3 17.2 62.5 61.4 -37.5 -25.5 -201 D36 2 439 C3t 27.7 51.7 20.6 61.7 36.6 1.7 22.8 19.6 57.6 56.6 -37.5 -26.1 -204 D37 2 417 C3t 23.6 48.2 28.2 53.4 41.9 4.6 17.6 16.5 65.9 64.4 -37.9 -25.2 -197 D38 2 557 C3t 22.5 48.9 28.6 55.0 42.0 3.0 21.8 17.3 60.9 59.8 -37.7 -25.0 -195 D39 2 570 C3t 21.7 44.6 33.8 47.4 45.7 6.9 19.5 16.2 64.3 62.9 -37.8 -24.8 -197 D40 2 795 C3t 24.9 51.6 23.5 58.2 41.1 0.7 21.7 12.6 65.7 64.6 -38.0 -25.3 -205 D41 2 453 C3t 26.2 54.3 19.5 62.7 36.7 0.7 22.6 11.6 65.8 64.7 -37.8 -25.1 -204 D42 2 455 C3t 25.5 49.8 24.7 56.4 43.6 - 21.6 12.2 66.3 65.2 -37.7 -24.9 -205 D43 2 466 C3t 24.4 51.5 24.1 55.4 43.5 1.1 19.5 10.4 70.2 68.9 -37.8 -25.2 -204 D44 2 462 C3t 20.8 52.6 26.6 57.6 41.7 0.7 19.3 15.2 65.5 64.4 D45 C3t 27.4 54.5 18.1 65.2 34.4 0.5 29.0 13.7 57.3 56.5 -37.2 -25.4 -198 
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表 2 大牛地气田上古生界天然气轻烃地球化学特征参数
Table 2. Typical geochemical parameters of light hydrocarbons in natural gas from Upper Paleozoic, Daniudi Gas Field
井号 层位 庚烷值/% 异庚烷值 2, 4-二甲基戊烷/2, 3-二甲基戊烷 气源岩最大埋深温度/℃ 苯/正己烷 苯/环己烷 正庚烷/甲基环己烷 甲苯/正庚烷 K1 P2/C7/% N2/C7/% P3/C7/% K2 D1 P1x 8.18 1.18 0.777 136.2 0.076 0.099 0.205 0.005 1.09 13.76 8.83 7.61 0.34 D2 P1x 12.50 2.44 0.771 136.1 0.101 0.140 0.406 0.012 1.09 21.26 6.66 10.91 0.39 D3 P1x 7.18 1.19 0.844 137.5 0.115 0.138 0.183 0.136 1.04 13.83 8.82 8.54 0.38 D4 P1x 18.53 4.48 0.966 139.5 0.028 0.093 0.905 - 1.09 28.30 5.27 15.11 0.45 D5 P1x 22.67 2.73 1.068 141.0 0.025 0.080 0.932 0.012 1.09 23.02 6.11 9.09 0.31 D6 P1x 9.28 1.58 0.849 137.5 0.048 0.071 0.406 - 1.15 20.89 10.06 10.58 0.34 D7 P1x 19.23 2.55 0.815 136.9 0.050 0.098 0.630 0.002 1.09 20.39 6.20 9.04 0.34 D8 P1x 8.73 1.33 0.976 139.6 0.029 0.052 0.258 0.007 1.06 16.54 9.33 9.06 0.35 D9 P1x 19.07 2.86 0.777 136.2 - - 0.629 - 1.07 20.84 5.38 9.53 0.36 D10 P1x 6.31 1.14 0.799 136.6 0.039 0.050 0.169 - 1.06 13.70 9.19 8.95 0.39 D11 P1x 13.49 2.90 0.666 133.9 0.096 0.101 0.403 - 1.10 20.05 5.84 10.74 0.41 D12 P1x 24.31 2.74 0.629 133.0 0.007 0.024 0.799 0.003 1.06 18.49 4.91 10.35 0.44 D13 P1x 6.24 2.19 0.732 135.3 - - 0.168 0.031 1.05 18.27 6.96 10.81 0.43 D14 P1x 17.59 3.23 1.074 141.1 - - 1.026 - 1.08 26.82 6.38 13.29 0.40 D15 P1x 8.10 2.10 0.660 133.8 - - 0.233 - 1.06 17.55 6.72 11.36 0.47 D16 P1x 19.67 4.81 0.741 135.5 - - 0.809 - 1.06 26.25 4.52 13.81 0.45 D17 P1x 8.79 1.37 0.923 138.8 - - 0.271 - 1.02 16.12 8.81 10.06 0.40 D18 P1x 8.13 2.20 0.767 136.0 - - 0.230 - 1.09 18.47 6.82 11.06 0.44 D19 P1x 13.99 3.45 0.766 136.0 - - 0.447 - 1.06 22.33 5.68 11.79 0.42 D20 P1x 16.13 2.84 0.674 134.1 - - 0.522 - 1.10 21.10 5.56 11.23 0.42 D21 P1x 12.05 2.79 0.686 134.3 - - 0.361 - 1.06 19.24 5.73 12.22 0.49 D22 P1s 10.24 1.49 0.896 138.4 0.050 0.090 0.301 0.053 1.08 17.12 8.41 9.21 0.36 D23 P1s 10.10 1.45 0.839 137.4 0.150 0.227 0.304 0.011 1.07 16.32 8.46 9.49 0.38 D24 P1s 6.69 1.46 0.588 132.0 0.711 0.507 0.163 0.651 1.13 13.31 7.14 7.70 0.38 D25 P1s 8.49 1.31 0.928 138.9 0.114 0.162 0.258 0.004 1.00 14.80 8.64 12.79 0.55 D26 P1s 10.61 1.84 0.837 137.3 0.054 0.092 0.280 0.006 1.09 16.03 6.24 8.09 0.36 D27 P1s 8.73 1.64 0.785 136.4 0.238 0.263 0.233 0.008 1.09 16.21 7.75 8.91 0.37 D28 P1s 9.23 1.54 0.898 138.4 0.164 0.220 0.333 0.139 1.10 18.88 9.24 10.14 0.36 D29 P1s 5.52 1.50 0.748 135.6 0.210 0.148 0.131 - 1.02 13.60 7.28 10.09 0.48 D30 P1s 6.35 1.79 0.673 134.1 - - 0.165 - 1.05 16.01 7.35 10.11 0.43 D31 P1s 6.24 1.41 0.876 138.0 0.096 0.172 0.276 - 1.10 14.29 8.33 9.09 0.40 D32 P1s 6.96 1.75 0.677 134.2 - - 0.180 - 1.10 15.85 7.23 9.85 0.43 D33 P1s 9.75 1.22 0.537 130.7 0.036 0.044 0.232 - 1.14 12.87 7.87 5.16 0.25 D34 P1s 7.79 1.32 0.840 137.4 0.058 0.080 0.206 - 1.08 14.43 8.62 7.90 0.34 D35 C3t 9.79 2.01 0.745 135.6 0.252 0.330 0.275 - 1.10 17.87 7.09 9.55 0.38 D36 C3t 10.62 1.99 0.805 136.7 0.123 0.187 0.341 0.004 1.08 18.69 7.00 10.67 0.42 D37 C3t 9.74 2.22 0.700 134.6 0.432 0.481 0.250 0.015 1.07 17.71 6.52 9.19 0.38 D38 C3t 10.12 2.28 1.308 144.0 0.305 0.324 0.285 0.008 1.07 22.50 7.50 7.50 0.25 D39 C3t 9.31 1.99 0.644 133.4 0.762 0.587 0.252 0.007 1.10 17.79 6.90 8.89 0.36 D40 C3t 6.98 1.95 0.788 136.4 0.055 0.067 0.192 0.016 1.05 17.59 7.07 9.62 0.39 D41 C3t 6.32 1.90 0.781 136.3 0.047 0.069 0.176 0.027 1.09 16.75 7.26 10.22 0.43 D42 C3t 6.87 1.79 0.799 136.6 - - 0.184 0.007 1.04 16.68 7.41 8.79 0.36 D43 C3t 6.01 1.93 0.774 136.2 0.094 0.106 0.148 0.014 1.07 16.25 6.76 8.79 0.38 D44 C3t 8.74 2.35 0.625 133.0 0.076 0.079 0.232 - 1.11 18.69 7.06 11.10 0.43 D45 C3t 7.12 1.60 0.742 135.5 0.035 0.059 0.239 - 1.10 16.10 7.66 12.42 0.52 注：气源岩最大埋深温度[T=140+15ln(2, 4-二甲基戊烷/2, 3-二甲基戊烷)][17]；K1=(2-甲基己烷+2, 3-二甲基戊烷)/(3-甲基己烷+2, 4-二甲基戊烷)[25]；P2、N2、P3分别为2-甲基己烷+3-甲基己烷、1, 1-二甲基环戊烷+1, 顺, 3-二甲基环戊烷+1, 反, 3-二甲基环戊烷、各类二甲基戊烷+3-乙基戊烷[26]；K2=P3/(P2+N2)，即：(各类二甲基戊烷+3-乙基戊烷)/(2-甲基己烷+3-甲基己烷+1, 1-二甲基环戊烷+1, 顺, 3-二甲基环戊烷+1, 反, 3-二甲基环戊烷)[26]。
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