珠江口盆地白云凹陷原油中典型生物标志化合物组合及其地球化学意义

冉子超; 李美俊; 李友川; 时阳; 王宁; 杨永才; 卢晓林; 肖洪

doi:10.11781/sysydz2022061059

珠江口盆地白云凹陷原油中典型生物标志化合物组合及其地球化学意义

doi: 10.11781/sysydz2022061059

冉子超^1,,
李美俊^{1, 2, ,},
李友川³,
时阳⁴,
王宁⁵,
杨永才³,
卢晓林¹,
肖洪¹

1.
中国石油大学(北京) 油气资源与探测国家重点实验室，地球科学学院，北京 102249
2.
长江大学油气资源与勘探技术教育部重点实验室，资源与环境学院，武汉 430100
3.
中海油研究总院有限责任公司，北京 100027
4.
中国石油南方石油勘探开发有限责任公司勘探开发研究中心，海口 570216
5.
中海油能源发展股份有限公司工程技术分公司中海油实验中心(深圳)，广东惠州 516000

基金项目:

中海石油(中国)有限公司北京研究中心与中国石油大学(北京)的合作项目“白云凹陷有效烃源岩灶研究” CCL2020RCPS0039ESN

详细信息

作者简介:
冉子超(1997—)，男，博士研究生，从事油气地球化学研究。E-mail：ranzichao@126.com

通讯作者:
李美俊(1972—)，男，博士，教授，从事油气地球化学研究。E-mail：meijunli@cup.edu.cn

中图分类号: TE122.114
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出版历程
- 收稿日期: 2021-07-29
- 修回日期: 2022-10-18
- 刊出日期: 2022-11-28

Biomarker compositions and geochemical significance of crude oils of Baiyun Sag, Pearl River Mouth Basin

1.
State Key Laboratory of Petroleum Resources and Prospecting, College of Geosciences, China University of Petroleum (Beijing), Beijing 102249, China
2.
Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, College of Resources and Environment, Yangtze University, Wuhan, Hubei 430100, China
3.
CNOOC Research Institute Company Limited, Beijing 100027, China
4.
Exploration and Development Research Center of PetroChina South Petroleum Exploration and Development Co., Ltd., Haikou, Hainan 570216, China
5.
CNOOC Experimental Center of Engineering Technology Branch of CNOOC Energy Development Co., Ltd. (Shenzhen), Huizhou, Guangdong 516000, China

摘要

摘要: 珠江口盆地白云凹陷原油中富含新C₁₅倍半萜烷、特殊构型的三环萜烷和四环萜烷(X、Y、Z和X1、Y1、Z1)及双杜松烷等指示陆源高等植物有机质输入的典型生物标志化合物以及常见的指示被子植物有机质输入的生物标志化合物奥利烷。基于白云凹陷13件原油样品饱和烃色谱质谱分析结果，对原油中典型生物标志化合物的组成及其地球化学意义进行了探讨。研究表明，降A-奥利烷(Y1)和C₂₇四环萜烷(Z1)可能具有相同的生物来源；而根据相关化合物分子结构及各区域丰度相关性分析，判断出新C₁₅倍半萜烷、降A-奥利烷和C₂₇四环萜烷及双杜松烷可能具有不同的生源或演化过程。另外，不同区域原油的生物标志化合物组成差异明显。这些生物标志化合物是研究区原油族群划分的良好指标。经分析，双杜松烷与新C₁₅倍半萜烷的分布受到沉积环境的影响较大，可能更富集于偏氧化的沉积环境；降A-奥利烷、C₂₇四环萜烷和奥利烷的分布主要受到生源的影响，而受沉积环境影响较小。白云东北、东区原油降A-奥利烷、C₂₇四环萜烷和奥利烷相对丰度明显偏高，这在一定程度上反映了位于白云东部的东沙隆起和云荔低隆起可能是研究区陆源有机质的重要来源地。
- 生物标志化合物 /
- 新C₁₅倍半萜烷 /
- 三环萜烷 /
- 四环萜烷 /
- 双杜松烷 /
- 原油 /
- 白云凹陷 /
- 珠江口盆地
Abstract: Crude oils from the Baiyun Sag of Pearl River Mouth Basin have high abundance of diagnostic biomarkers including novel C₁₅ sesquiterpene, special configurated tricyclic sesquiterpenes and tetracyclic sesquiterpenes (X, Y, Z and X1, Y1, Z1), and bicadinanes, which indicate the contributions from terrestrial higher plants to the organic matters. These oils are also rich in oleanane, which is a diagnostic biomarker for angiosperm organic matter. Based on the analysis of 13 crude oils from the Baiyun Sag, the compositions and geochemical significance of typical biomarkers were revealed. Results indicate that C₂₄-des-oleanane (Y1) and C₂₇ tetracyclic (Z1) may share a similar biological origin. Novel C₁₅ sesquiterpene, C₂₄-des-oleanane and C₂₇ tetracyclic, and bicadinanes may be derived from different higher plants according to the molecular structure and abundance correlation analysis of the related compounds. In addition, the biomarker compositions of crude oils from different regions are significantly varied, which will benefit the oil group classification in the Baiyun Sag. The distribution of novel C₁₅ sesquiterpene and bicadinanes was influenced by sedimentary environment, and may be more enriched in oxidized environment. The distribution patterns of C₂₄-des-oleanane, C₂₇ tetracyclic and oleanane are principally affected by biogenic input, but are less influenced by sedimentary environment fluctuation. The relatively high abundance of C₂₄-des-oleanane, C₂₇ tetracyclic and oleanane in the crude oil in the northeastern and eastern Baiyun area reflects that the Dongsha Uplift and the Yunli Low Uplift may be an important source of terrigenous organic matter in this area.
- biomarker /
- novel C₁₅ sesquiterpene /
- tricyclic sesquiterpenes /
- tetracyclic sesquiterpenes /
- bicadinanes /
- crude oil /
- Baiyun Sag /
- Pearl River Mouth Basin

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图 1 珠江口盆地白云凹陷构造单元划分及地层分布

Figure 1. Tectonic units and stratigraphic column of Baiyun Sag, Pearl River Mouth Basin

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图 2 珠江口盆地白云凹陷原油中倍半萜烷分布特征(m/z 123)(a、b)及新C₁₅倍半萜烷A(c)、B(d)质谱图

A+B为新C₁₅倍半萜烷 A+新C₁₅倍半萜烷 B；C为重排补身烷 C；D为重排补身烷 D

Figure 2. Distributions of C₁₅ sesquiterpanes (m/z 123) (a, b) and mass spectra with structure chart of novel C₁₅ sesquiterpanes A (c) and B (d) in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 3 珠江口盆地白云凹陷原油中三环及四环萜烷分布特征(m/z 191) 和X(c)、Y(d)、Z(e)、X1(f)、Y1(g)、Z1(h)化合物质谱图

C₂₆TT(20S)和C₂₆TT(20R)为2个构型的C₂₆三环萜烷；C₂₄TeT为C₂₄四环萜烷

Figure 3. Distributions of tricyclic, tetracyclic terpanes (m/z 191) (a, b) and mass spectra with structure chart of X (c), Y (d), Z (e), X1 (f), Y1 (g), and Z1 (h) compounds in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 4 珠江口盆地白云凹陷双杜松烷分布特征(m/z 412)及双杜松烷W(c)、T(d)质谱图

R 为双杜松烷W和T的异构体；OL 为奥利烷；C₃₀H为C₃₀藿烷

Figure 4. Distributions of bicadinanes (m/z 412) (a, b) and mass spectra with structure chart of bicadinanes W (c) and T (d) in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 5 珠江口盆地白云凹陷原油Ph/nC₁₈与Pr/nC₁₇相关图(a)及三环萜烷相对含量三角关系图(b)

Figure 5. Plot of Ph/nC₁₈-Pr/nC₁₇ (a) and relative content of tricyclic terpenes (b) in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 6 珠江口盆地白云凹陷奥利烷与姥植比相关图

Figure 6. Oleanane vs. Pr/Ph in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 7 珠江口盆地白云凹陷原油中新C₁₅倍半萜烷与奥利烷(a)、新C₁₅倍半萜烷与姥植比(b)相关图

Figure 7. Novel C₁₅ sesquiterpanes (A+B)/(C+D) vs. OL/C₃₀H (a), novel C₁₅ sesquiterpanes (A+B)/(C+D) vs. Pr/Ph in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 8 珠江口盆地白云凹陷原油中降A-奥利烷(Y1)与奥利烷(a)、C₂₇四环萜烷(Z1)与奥利烷(b)、降A-奥利烷(Y1)与C₂₇四环萜烷(Z1)(c)、C₂₇四环萜烷(Z1)与姥植比(d)相关图

Figure 8. C₂₄-des-oleanane (Y1) vs. oleanane (a), C₂₇ tetracyclic (Z1) vs. oleanane (b), C₂₄-des-oleanane (Y1) vs. C₂₇ tetracyclic (Z1) (c) and C₂₇ tetracyclic (Z1) vs. Pr/Ph (d) in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 9 珠江口盆地白云凹陷原油中双杜松烷与奥利烷(a)、双杜松烷与姥植比(b)相关图

Figure 9. Bicadinanes vs. oleanane (a), and bicadinanes vs. Pr/Ph (b) in crude oil from Baiyun Sag, Pearl River Mouth Basin

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图 10 珠江口盆地白云凹陷原油族群划分

Figure 10. Division of oils' families from Baiyun Sag, Pearl River Mouth Basin

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图 11 珠江口盆地白云凹陷原油族群划分及奥利烷类相关先质物的输入方向

Figure 11. Division of crude oil population and biogenic input direction of oleanane precursors from Baiyun Sag, Pearl River Mouth Basin

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表 1 珠江口盆地白云凹陷各区原油生物标志化合物地化指标参数

Table 1. Biomarker parameters of oil from wells in Baiyun Sag, Pearl River Mouth Basin

地化指标	北坡				东北区						东区
地化指标	N-1	N-2	N-3	N-4	NE-1	NE-2	NE-3	NE-4	NE-5	NE-6	E-1	E-2	E-3
Pr/Ph	4.77	7.10	5.58	6.40	6.27	5.49	6.15	4.32	4.58	4.68	4.24	3.32	3.54
Pr/nC₁₇	1.08	1.41	1.51	1.67	1.10	1.09	1.12	1.36	1.08	1.08	0.78	0.61	0.63
Ph/nC₁₈	0.23	0.25	0.29	0.27	0.21	0.23	0.21	0.34	0.27	0.26	0.21	0.19	0.20
OL/C₃₀H	0.43	0.98	0.41	0.38	0.99	0.91	0.91	0.98	0.94	0.74	1.09	1.17	0.85
(A+B)/(C+D)	0.74	0.94	0.65	1.06	0.90	1.04	1.11	0.64	0.69	0.48	0.53	0.36	0.50
(W+T)/C₃₀H	5.01	5.80	6.17	8.61	5.72	5.92	6.79	2.63	2.78	2.60	4.05	2.69	2.14
Y1/(Y1+C₂₄TT)	0.80	0.90	0.84	0.77	0.93	0.94	0.91	0.82	0.88	0.86	0.88	0.90	0.87
Z1/(Z1+C₂₄TT)	0.49	0.73	0.44	0.36	0.69	0.78	0.69	0.62	0.74	0.70	0.62	0.74	0.71
C₁₉₊₂₀TT/%	58.60	67.20	65.61	64.24	67.52	65.41	60.23	69.87	62.20	58.74	62.26	54.59	75.12
C₂₁TT/%	25.77	20.04	23.00	21.08	18.09	19.48	20.41	18.73	20.56	20.80	20.84	21.84	12.29
C₂₃TT/%	15.64	12.76	11.39	14.68	14.39	15.11	19.36	11.40	17.23	20.46	16.91	23.57	12.59
注：Pr为姥鲛烷；Ph为植烷；nC₁₇为正构十七烷；nC₁₈为正构十八烷；OL为奥利烷；C₃₀H为C₃₀藿烷；A为新C₁₅倍半萜烷A；B为新C₁₅倍半萜烷B；C为重排补身烷C；D为重排补身烷D；Y1为降A-奥利烷；Z1为C₂₇四环萜烷；TT表示三环萜烷。

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