影响海相烃源岩热解生烃过程的地质条件

郑伦举; 关德范; 郭小文; 马中良

doi:10.3799/dqkx.2015.075

影响海相烃源岩热解生烃过程的地质条件

doi: 10.3799/dqkx.2015.075

郑伦举^{1, 2,},
关德范¹,
郭小文^3, ,,
马中良^{1, 2}

1.
中国石化油气成藏重点实验室，江苏无锡 214151
2.
中国石化石油勘探开发研究院无锡石油地质研究所，江苏无锡 214151
3.
中国地质大学构造与油气资源教育部重点实验室，湖北武汉 430074

基金项目:

国家重点基础研究发展计划“973”项目 2005CB422102

国家自然科学基金项目 41302110

中国石化科技开发部项目 P11060

详细信息

作者简介:
郑伦举(1966-)，男，高级工程师，博士，从事油气地球化学和石油地质实验研究.E-mail: zhenglj.syky@sinopec.com

通讯作者:
郭小文，E-mail: cuggxw@163.com

中图分类号: P618.13
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出版历程
- 收稿日期: 2014-10-10
- 刊出日期: 2015-05-15

Key Geological Conditions Affecting Pyrolysis Experiments of Marine Source Rocks for Hydrocarbon Generation

Zheng Lunju^{1, 2
,},
Guan Defan¹,
Guo Xiaowen^{3
, ,},
Ma Zhongliang^{1, 2}

1.
Key Laboratory of Petroleum Accumulation Mechanisms, SINOPEC, Wuxi 214151, China
2.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi 214151, China
3.
Key Laboratory of Tectonics and Petroleum Resources of the Ministry of Education, China University of Geosciences, Wuhan 430074, China

摘要

摘要: 热解生烃实验是研究油气生成机理与定量评价烃源岩生烃潜力的重要方法.烃源岩热解生烃模拟结果不仅与温度、压力和时间等因素有关，而且与地层孔隙水及压实成岩作用等地质因素密切相关.采用高压流体和高压釜(低压水蒸气)两种生烃热模拟方法对低成熟海相二叠统大隆组(P₂d)黑色泥岩进行了热解生烃实验模拟.对比分析两组实验结果表明地层孔隙热解实验有利于液态油的生成，不利于液态油向气态烃的转化，并极大地提高了干酪根的生油气潜力，显示了高压液态水、流体压力和孔隙空间等地质因素对烃源岩中有机质热成熟生烃反应的重要影响.这种影响可能与高压液态水的近临界特性有关，近临界特性地层水的参与改变了干酪根热力生烃反应的物理化学行为.推断在实际地质温压(100~200 ℃，30~120 MPa)条件下，烃源岩孔隙中的地层水是一种相对低温高压液态水，具有水的近临界物理化学特性，因此高压流体生烃热模拟实验与实际地层情况更为接近，能更有效地评价烃源岩生烃潜力.
- 生烃热模拟 /
- 高压液态水 /
- 流体压力 /
- 孔隙空间 /
- 生烃潜力 /
- 石油地质 /
- 烃类
Abstract: Hydrocarbon generation simulation experiment (pyrolysis) is important for studying petroleum generation mechanisms and quantitatively estimating hydrocarbon generation potential of source rocks. The simulation experiment results not only depend on the temperature, pressure and duration, but also on the pore fluid, source rock compaction. In this paper, marine black mudstone with low maturity from the Permian Dalong Formation (P₂d) is used for hydrocarbon generation simulations with two types of high-pressure liquid water and low-pressure water steam. The results show that the high-pressure liquid water can increase the organic matter petroleum generation potential greatly, enhancing oil generation and retarding the transformation from oil to gas, suggesting important influence of geological factors such as high-pressure liquid water, fluid pressure and pore space on the hydrocarbon generation of the source rocks. The increase of the petroleum generation potential is due to the fact that the physicochemistry reaction of the kerogen is greatly enhanced at the presence of the near-critical properties water. It is concluded that the water in the pore space of the source rocks is of the high-pressure and low-temperature liquid water in the subsurface temperature (100-200 ℃) and pressure (30-120 MPa) conditions, which has the properties of near-critical water. Therefore, the hydrocarbon generation simulation experiment (pyrolysis) with high-pressure liquid water is more close to the actual geological conditions than that of the low pressure water steam and could be used to estimate hydrocarbon generation potential of source rock more effectively.
- pyrolysis simulation experiment /
- high-pressure liquid water /
- fluid pressure /
- pore space /
- hydrocarbon generation potential /
- petroleum geology /
- hydrocarbon

HTML全文

图 1 两种热解生烃模拟实验仪的原理结构示意

图 1a：FPS热解生烃模拟实验仪；1.液压控制系统；2.温度传感器；3.高压反应釜；4.油缸A；5.油缸B；6.箱式电热炉；7.四通阀；8.压力传感器；9.高压气动阀；10.二位三通电磁阀；11.减压阀；12.气瓶；13.气液分离器；14.冷阱；15.真空表；16.电动阀；17.储气室；18.活塞容器；19.截止阀；20.高压器；21.真空泵；22.压力表；23.三通阀.图 1b：CPS热解生烃模拟实验仪；1.箱式电热炉；2.样品；3.传感器探头；4.高压反应釜；5.温度传感器；6.压力传感器；7.四通阀；8.截止阀；9.真空泵；10.气液搜集器；11.杜瓦瓶冷阱；12.气体定量瓶；13.高低瓶；14.排水集气瓶；15.控制器

Fig. 1. The principle sketch of the two physical simulation apparatus for the hydrocarbon generation

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图 2 两种热解实验氢气产率与R_o关系曲线

Fig. 2. Relationship between the H₂ generation rate and R_o for the two types of pyrolysis simulation experiments

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图 3 两种热解实验烃气产率与R_o关系曲线

Fig. 3. Relationship between the hydrocarbon gas generation rate and R_o for the two types of pyrolysis simulation experiments

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图 4 两种热解实验CO₂产率与R_o关系

Fig. 4. Relationship between the CO₂ production and R_o for the two types of pyrolysis simulation experiments

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图 5 两种热解实验加热温度与镜质体反射率的关系

Fig. 5. Relationship between the pyrolysis temperature and R_o for the two types of pyrolysis simulation experiments

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图 6 两种热解实验加热温度与固体残渣氢指数关系

Fig. 6. Relationship between the pyrolysis temperature and Hydrogen index for the two types of pyrolysis simulation experiments

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图 7 两种热解实验沥青/油产率与镜质体反射率的关系

Fig. 7. Relationship between the bitumen/oil generation rate and R_o for the two types of pyrolysis simulation experiments

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表 1 两种不同模拟方式的实验边界条件

Table 1. Experiments boundary conditions for the two types of pyrolysis simulation experiments

模拟方式	模拟温度(℃)	恒温时间(h)	静岩压力(MPa)		流体压力(MPa)		加水量(mL)		生烃空间(mL)
序号			FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS
1	250	48	43	0	19.8	5.9	21	10	21	450
2	275	48	47	0	22.7	-	21	-	21	-
3	300	48	58	0	27.4	8.6	21	10	21	450
4	325	48	66	0	30.6	11.8	20	10	21	450
5	350	48	71	0	34.5	13.4	19	10	21	450
6	370	48	75	0	37.9	17.1	17	10	21	450

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表 2 两种热解实验条件下气体组分数据

Table 2. Gas components for the two types of pyrolysis simulation experiments

热解方式	热解温度(℃)
	250		275	300		325		350		370
	FPS	CPS	FPS	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS
H₂	0.49	73.94	11.67	14.46	76.76	9.83	53.56	0.78	43.95	0.42	39.81
CO₂	3.89	14.79	32.47	30.65	11.22	34.34	27.33	23.05	26.99	22.65	26.55
CH₄	0.31	5.62	15.33	30.56	8.95	30.13	10.42	42.55	13.77	43.19	16.74
C₂H₆	0.03	0.50	2.10	14.21	0.62	14.33	4.46	21.33	7.13	20.16	7.65
C₂H₄	0.00	0.16	0.03	0.01	0.22	0.01	0.13	0.01	0.10	0.00	0.05
C₃H₈	0.01	0.14	0.98	4.14	0.18	4.85	1.68	7.83	3.42	8.45	4.34
C₃H₆	0.01	0.09	0.05	0.02	0.11	0.03	0.29	0.02	0.39	0.02	0.22
iC₄H₁₀	0.00	0.01	0.13	0.36	0.01	0.57	0.19	0.91	0.49	1.08	0.69
nC₄H₁₀	0.00	0.03	0.27	0.68	0.03	1.50	0.51	1.86	1.14	2.19	1.67
C₄H₈	0.00	0.01	0.02	0.00	0.01	0.01	0.07	0.01	0.13	0.01	0.11
iC₅H₁₂	0.00	0.00	0.06	0.08	0.01	0.34	0.11	0.30	0.24	0.37	0.42
nC₅H₁₂	0.00	0.01	0.05	0.04	0.01	0.36	0.14	0.23	0.32	0.27	0.51
C₆⁺	0.00	0.03	0.06	0.01	0.04	0.30	0.25	0.05	0.65	0.06	0.55
C₁/(C₁-C₄)	0.85	0.85	0.80	0.61	0.88	0.57	0.57	0.57	0.50	0.57	0.51

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表 3 两种热解实验气体与沥青产率值

Table 3. Gas and bitumen generation rates in the two types of pyrolysis simulation experiments

热解温度(℃)	R_o(%)		CO₂产率 (mL/g)		H₂产率 (mL/g)		烃气产率 (mg/g)		沥青/油产率 (mg/g)
	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS
250	0.58	0.61	1.25	1.89	0.28	12.38	0.18	1.15	68.06	13.53
275	0.62	-	1.16	-	0.42	-	0.63	-	102.79	-
300	0.75	0.78	0.90	2.26	0.42	15.44	1.53	1.69	207.06	65.18
325	0.84	0.96	3.04	18.36	0.87	35.98	5.24	14.24	361.39	215.65
350	1.02	1.15	9.14	32.89	0.31	53.57	33.19	43.72	376.56	161.37
370	1.21	1.36	10.92	56.54	0.20	84.79	41.21	91.13	358.44	95.36

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表 4 两种热解实验固体残样岩石热解参数

Table 4. Rock pyrolysis data for the residues in the two types of pyrolysis simulation experiments

温度(℃)	R_o(%)		S₁(mg/g)		S₂(mg/g)		T_max(℃)		PC(%)		TOC(%)		HI(mg/g)
	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS	FPS	CPS
250	0.58	0.61	1.79	1.35	39.78	40.25	437	435	3.47	3.42	12.32	12.04	323	334
275	0.62	1.20	-	40.94	-	435	-	3.52	-	11.98	-	342	-	-
300	0.75	0.78	2.42	0.40	32.65	37.96	439	437	2.93	3.24	10.31	11.85	317	320
325	0.84	0.96	3.08	4.51	29.58	30.13	439	440	2.74	2.91	9.39	11.7	315	258
350	1.02	1.15	6.64	3.19	18.08	14.19	441	451	1.67	1.46	11.59	10.95	156	130
370	1.21	1.36	5.77	1.97	10.23	5.90	441	458	1.34	0.67	10.57	10.54	97	56

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