Formation Water of Near-Critical Properties and Its Effects on the Processes of Hydrocarbon Generation and Expulsion
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摘要: 研究利用特制的地层孔隙热压模拟实验装置, 开展了模拟地层孔隙空间高压液态水热体系烃源岩生排烃模拟实验.模拟实验施加的流体压力为38±2 MPa, 温度为290~390 ℃.模拟实验结果显示了有关高压液态水及其与之相联系的流体压力和孔隙空间等因素对烃源岩生排烃影响作用的一些重要现象, 实验发现高压液态水介质条件有利于液态油的生成和保存, 不利于液态油向气态烃的转化, 而且干酪根的生烃潜力和排油效率有一定的提高.这些新的实验现象可能主要与近临界特性的高压液态地层水的作用有关, 进一步推断近临界特性的高压液态水参与干酪根向油气的转化反应, 增加了水对油气的溶解能力.在地下实际烃源岩生排烃的温压(100~200 ℃, 30~120 MPa)条件下, 岩石孔隙中的地层水是一种相对低温高压压缩液态水, 这种地层水可能具有近临界特性, 对烃源岩生排烃过程有重要影响.但目前对这种现象的机理和石油地质意义还知之较少.因此, 加强高压地层水近临界条件下烃源岩生排烃热压模拟实验研究, 对进一步深入理解地层条件下的近临界水介质、流体压力、孔隙空间因素对生排烃过程的影响, 深化烃源岩生排烃机理的探讨, 建立地质尺度上的烃源岩生排烃动力学模型, 都具有重要的理论和实际意义.Abstract: A special simulation experimental device using a high pressure liquid water system in the similar geological pore space with fluid pressures around 38±2 MPa and temperatures ranging from 290 ℃ to 390 ℃ is used to simulate hydrocarbon generation and expulsion from source rocks in this study. The new experimental results show many important phenomena about the generation and expulsion influenced by high-pressure liquid water linking with fluid pressure and pore space. It is found that high-pressure liquid water medium condition facilitates the generation and preservation of liquid oil and improves the potential of hydrocarbon generation from kerogen and the efficiency of oil expulsion but it is not conducive to the conversion of liquid hydrocarbon to gaseous hydrocarbon. It is considered that these new experimental phenomena may be mainly related to the effects of high-pressure liquid water of near-critical properties. It is further inferred that the high-pressure liquid water of near-critical characteristics is involved in the conversion of kerogen to oil and gas reactions, to increase the solubility of the oil and gas in water. Under the appropriate geological conditions, hydrocarbon generation and expulsion from source rocks occur at temperatures ranging from 100 ℃ to 200 ℃ and pressures ranging from 30 MPa to 120 MPa in most cases, suggesting that actual formation pore water could be a compressed state liquid water with near-critical properties at a relatively low temperature and high-pressure environment. This high-pressure liquid water of near-critical characteristics may have important effect on the processes of petroleum generation and expulsion. However, the mechanism and geological significance for petroleum exploration of these phenomena are still not clear. Further studies are necessary for such simulation experiments under high pressure liquid water condition for better understanding of the actual roles of the factors such as the near-critical water medium, fluid pressure and pore space. It is believed that this study may assist to establish the improving models of dynamics of hydrocarbon generation and expulsion in geological scale.
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图 1 几种主要生排烃模拟方式的反应空间与介质、样品间关系示意
a.无限空间热解生烃；b.密闭空间热解生烃；c.地层孔隙空间热解生烃
Fig. 1. Diagram of several main simulation devices of hydrocarbon generation and expulsion showing the relationships between reaction space and media, sample
图 2 两种加压流体介质对排出油、残留油和总油产率的影响
a.表示高压液态水介质；b.表示氮气+水蒸汽介质
Fig. 2. The yields of discharge oil, residual oil and total oil influenced by two pressurized fluid mediums
表 1 高温高压液态水与氮气+水蒸汽介质的气油产率对
Table 1. The yields of gas and oil under high temperature/pressure water medium and nitrogen medium
流体介质 模拟温度(℃) Ro(%) CO2(m3/TOC) H2(m3/TOC) 烃气(kg/TOC) 排出油(kg/TOC) 残留油(kg/TOC) 总油(kg/TOC) 总烃(kg/TOC) 290 0.78 3.06 0.31 0.90 3.01 14.90 17.91 18.81 320 0.94 17.46 0.04 5.94 16.75 33.37 50.12 56.06 高温高压液态水a 340 1.13 20.27 0.04 10.33 32.47 30.39 62.86 78.19 370 1.56 28.51 0.12 39.31 45.53 16.38 61.91 101.21 390 1.94 39.94 0.17 58.78 44.60 1.56 46.16 104.94 290 0.71 32.70 0.10 1.47 1.05 9.98 11.03 12.49 320 0.84 29.99 0.20 18.56 5.91 22.41 28.32 46.88 高温高压氮气+水蒸汽 340 1.05 61.49 0.14 28.15 11.30 31.50 42.80 70.95 370 1.42 75.66 0.17 64.10 15.48 16.71 22.18 86.29 390 1.71 57.02 16.67 65.57 10.02 3.00 13.02 78.59 注：a.地层流体压力38 MPa；静岩压力80 MPa；生烃空间为9.5 mL. 
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表 2 高温高压下流体介质对残余固体热解参数的影响
Table 2. The pyrolysis data of the residual kerogen influenced by two fluid mediums under high pressure and temperature conditions
模拟温度(℃) S2-a(mg/g) S2-b(mg/g) Tmax-a(℃) Tmax-b(℃) PC-a(%) PC-b(%) TOC-a(%) TOC-b(%) HI-a(mg/g·c) HI-b(mg/g·c) 290 87.59 75.53 426 425 8.09 6.95 72.97 68.06 120 111 320 78.32 54.61 438 435 7.45 5.43 75.19 68.80 104 79 340 56.26 47.42 455 458 5.58 4.52 71.28 74.88 79 63 370 13.58 25.97 476 469 1.51 2.79 55.33 74.89 25 35 390 6.84 7.90 501 502 0.81 0.92 52.68 57.99 13 14 注：a.表示高压液态水介质；b.表示高压氮气+水蒸汽介质.
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