含油砂岩抽提物中含氮化合物指标的有效性分析

朱楠; 王爱国; 郭凯; 吴春燕; 李春雨; 杨泽光; 何森森

doi:10.11781/sysydz202402393

含油砂岩抽提物中含氮化合物指标的有效性分析

doi: 10.11781/sysydz202402393

朱楠^{1, 2,},
王爱国^{1, 2, ,},
郭凯^{1, 2},
吴春燕³,
李春雨^{1, 2},
杨泽光^{1, 2},
何森森^{1, 2}

1.
西北大学地质学系, 西安 710069
2.
西北大学大陆动力学国家重点实验室, 西安 710069
3.
陕西延长石油(集团)有限责任公司研究院, 西安 710075

基金项目:

国家自然科学基金 41402115

陕西省自然科学基础研究计划 2020JQ-591

详细信息

作者简介:
朱楠(2000—)，女，硕士生，能源地质学专业。E-mail: zhunan@stumail.nwu.edu.cn

通讯作者:
王爱国(1984—)，男，博士，教授，从事油气地球化学和油气运移成藏研究。E-mail: wag@nwu.edu.cn

中图分类号: TE135
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- 被引次数: 0
出版历程
- 收稿日期: 2023-05-15
- 修回日期: 2024-02-18
- 刊出日期: 2024-03-28

Effectiveness of nitrogen compound indices of oil-bearing sandstone extracts

ZHU Nan^{1, 2
,},
WANG Aiguo^{1, 2
, ,},
GUO Kai^{1, 2},
WU Chunyan³,
LI Chunyu^{1, 2},
YANG Zeguang^{1, 2},
HE Sensen^{1, 2}

1.
Department of Geology, Northwest University, Xi'an, Shaanxi 710069, China
2.
State Key Laboratory of Continental Dynamics, Northwest University, Xi'an, Shaanxi 710069, China
3.
Research Institute of Yanchang Petroleum(Group) Co. Ltd., Xi'an, Shaanxi 710075, China

摘要

摘要: 在油样匮乏地区鲜见利用含氮化合物示踪油气运移的报道，究其原因是含油砂岩抽提物中含氮化合物指标的有效性还不清楚，为此，设计了2组、5种抽提方法的对比实验，探讨了含氮化合物指标的有效性。实验结果显示，随着抽提强度的增大，抽提物的1-/4-甲基咔唑和1, 8-/2, 7-二甲基咔唑的比值逐渐减小，但始终高于对照石油；苯并咔唑[a]/[c]比值则保持相对稳定并接近对照石油。分析认为，导致这些现象的根本原因是咔唑类异构体吸附能力的差异。在地表条件下，该差异导致咔唑类异构体在游离烃—吸附烃之间发生分馏；在抽提时，该差异还导致它们在抽提物—岩石之间发生分馏。这2种分馏作用控制了含油砂岩抽提物中含氮化合物指标的变化。相较于1-/4-甲基咔唑和1, 8-/2, 7-二甲基咔唑，苯并咔唑[a]/[c]受这2种分馏作用的影响较小，比值的变化主要受控于运移分馏作用，所指示的油气运移方向也符合地质实际，因而成为含油砂岩抽提物中有效的含氮化合物指标，可将其用于油样匮乏地区的石油运移示踪研究。
- 含氮化合物 /
- 抽提实验 /
- 抽提物 /
- 含油砂岩 /
- 油气运移 /
- 油气地球化学
Abstract: Reports on the utilization of nitrogen compounds to trace oil and gas migration in oil-scarce regions are limited. This scarcity can be attributed to the lack of clarity regarding the effectiveness of nitrogen compound indices in oil-bearing sandstone extracts. To address this knowledge gap, two sets of experiments were designed, encompassing five extraction methods, to evaluate the validity of nitrogen compound indices. The results showed that as the extraction intensity increased, the ratios of 1-/4-methylcarbazole and 1, 8-/2, 7-dimethylcarbazole in the extracts gradually decreased but remained consistently elevated compared to the control oils. The benzocarbazole [a]/[c] ratio remained relatively stable and closely aligned with the control oils. Upon analysis, it was concluded that the observed variations could be attributed to the differing adsorption capacities of carbazole isomers. These differences lead to the fractionation of carbazole isomers between free and adsorbed hydrocarbons under surface conditions, as well as between the extracts and rocks during the extraction process. In comparison to 1-/4-methylcarbazole and 1, 8-/2, 7-dimethylcarbazole, the benzocarbazole [a]/[c] ratio is less susceptible to these two fractionations, with its variations primarily governed by migration fractionation. Additionally, the indicated direction of oil and gas migration aligns with geological realities. Therefore, the benzocarbazole [a]/[c] ratio can be considered an effective nitrogen compound index in oil-bearing sandstone extracts, suitable for oil migration tracing studies in oil-scarce regions.
- nitrogen compound /
- extraction experiment /
- extract /
- oil-bearing sandstone /
- petroleum migration /
- petroleum geochemistry
注释:

利益冲突声明/Conflict of Interests

所有作者声明不存在利益冲突。

All authors disclose no relevant conflict of interests.

作者贡献/Authors’Contributions

朱楠、王爱国、吴春燕参与研究设计；郭凯、李春雨、杨泽光、何森森完成样品采集工作和实验操作；朱楠、王爱国参与论文写作和修改。所有作者均阅读并同意最终稿件的提交。

The study was designed by ZHU Nan, WANG Aiguo and WU Chunyan. The sample collection and experimental operation were completed by GUO Kai, LI Chunyu, YANG Zeguang and HE Sensen. The manuscript was drafted and revised by ZHU Nan and WANG Aiguo. All the authors have read the last version of paper and consented for submission.

HTML全文

图 1 鄂尔多斯盆地A井和B井延长组原油和含油砂岩抽提物中咔唑类化合物含量对比

Figure 1. Percent of carbazole compounds in crude oil and oil-bearing sandstone extracts from Yanchang Formation of wells A and B in Ordos Basin

下载: 全尺寸图片幻灯片

图 2 鄂尔多斯盆地A井和B井延长组原油和含油砂岩抽提物中含氮化合物指标对比

MC.甲基咔唑；DMC.二甲基咔唑；[a]/[c].苯并咔唑[a]/[c]。

Figure 2. Comparison of nitrogen compound indices between crude oil and oil-bearing sandstone extracts from Yanchang Formation of wells A and B in Ordos Basin

下载: 全尺寸图片幻灯片

图 3 鄂尔多斯盆地陕北斜坡延长组石油与含油砂岩抽提物含氮化合物指标对比

Figure 3. Comparison of nitrogen compound indices between oil and oil-bearing sandstone extracts from Yanchang Formation of wells A and B in Ordos Basin

下载: 全尺寸图片幻灯片

图 4 鄂尔多斯盆地陕北斜坡含油砂岩抽提物的含氮化合物指标示踪石油运移方向对比

a.长6砂体展布及长7烃源岩范围(据文献[27-28]修改)；b-c.X和Y地区内[a]/[c]指示的石油运移方向；d-e.X和Y地区内1-/4-MC和1, 8-/2, 7-DMC比值分布。

Figure 4. Comparison of petroleum migration direction indicated by nitrogen compound indices in oil-bearing sandstone extracts from Shaanbei Slope of Ordos Basin

下载: 全尺寸图片幻灯片

图 5 鄂尔多斯盆地陕北斜坡含油砂岩抽提物的代表性总离子流(TIC)图

Figure 5. Representative total ion chromatogram (TIC) of oil-bearing sandstone extracts from Shaanbei Slope of Ordos Basin

下载: 全尺寸图片幻灯片

表 1 鄂尔多斯盆地A井和B井延长组原油及5种抽提含油砂岩方法对比

Table 1. Comparison of crude oil and five extraction methods for oil-bearing sandstones from Yanchang Formation of wells A and B in Ordos Basin

样号	深度/m	样品类型	粉碎粒径/mm	抽提方法	样品重量/g
A	2 294.76	原油			0.025~0.050
A-1	2 294.76	含油砂岩	0.15	①混合溶剂+索氏抽提	20
A-2	2 294.76	含油砂岩	0.15	②混合溶剂+超声波抽提	20
A-3	2 294.76	含油砂岩	5~10	③混合溶剂+超声波抽提	20
A-4	2 294.76	含油砂岩	0.15	④正己烷+超声波抽提	20
A-5	2 294.76	含油砂岩	5~10	⑤正己烷+超声波抽提	20
B	2 223.52	原油			0.025~0.050
B-1	2 223.52	含油砂岩	0.15	①混合溶剂+索氏抽提	20
B-2	2 223.52	含油砂岩	0.15	②混合溶剂+超声波抽提	20
B-3	2 223.52	含油砂岩	5~10	③混合溶剂+超声波抽提	20
B-4	2 223.52	含油砂岩	0.15	④正己烷+超声波抽提	20
B-5	2 223.52	含油砂岩	5~10	⑤正己烷+超声波抽提	20
注：表中混合溶剂为二氯甲烷∶甲醇(9∶1，体积比)。

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表 2 鄂尔多斯盆地A井和B井延长组原油和含油砂岩抽提物中咔唑类化合物含量

Table 2. Percent of carbazole compounds in crude oil and oil-bearing sandstone extracts of Yanchang Formation from well A and B in Ordos Basin %

样号	样品类型	咔唑	甲基咔唑	二甲基咔唑	三甲基咔唑	苯并咔唑	抽提物含量
A	原油	1.3	10.6	48.2	37.4	2.6
A-1	含油砂岩	18.0	17.4	43.2	16.4	5.2	0.12
A-2	含油砂岩	1.7	13.8	55.1	26.2	3.2	0.05
A-3	含油砂岩	1.6	14.1	55.0	25.1	4.2	0.06
A-4	含油砂岩	2.2	14.7	55.4	26.4	1.3	0.02
A-5	含油砂岩	2.7	15.6	55.3	24.6	1.8	0.03
B	原油	1.7	10.5	48.0	36.5	3.3
B-1	含油砂岩	3.3	23.6	50.6	17.5	5.0	0.81
B-2	含油砂岩	1.8	22.1	57.5	13.0	5.6	0.11
B-3	含油砂岩	1.7	24.1	57.2	10.2	6.9	0.08
B-4	含油砂岩	4.0	22.0	56.9	17.1	0.0	0.10
B-5	含油砂岩	3.6	21.6	59.4	15.4	0.0	0.08

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表 3 鄂尔多斯盆地A井和B井延长组原油及含油砂岩抽提物中含氮化合物指标

Table 3. Comparison of nitrogen compound indices between crude oil and oil-bearing sandstone extracts from Yanchang Formation of wells A and B in Ordos Basin

样号	样品类型	抽提方法	1-/4-MC	1, 8-/2, 7-DMC	[a]/[c]	1, 6-/1, 7-DMC	1, 3-/1, 6-DMC
A	原油		2.23	1.63	0.99	0.86	1.00
A-1	含油砂岩	①混合溶剂+索氏抽提	3.28	2.41	0.84	0.92	0.74
A-2	含油砂岩	②混合溶剂+超声波抽提	8.44	4.54	1.54	0.82	0.76
A-3	含油砂岩	③混合溶剂+超声波抽提	5.95	3.33	1.39	0.85	0.67
A-4	含油砂岩	④正己烷+超声波抽提	7.89	21.84	1.03	0.63	0.92
A-5	含油砂岩	⑤正己烷+超声波抽提	6.45	11.13	1.13	0.67	0.78
B	原油		2.88	1.92	1.58	0.85	0.98
B-1	含油砂岩	①混合溶剂+索氏抽提	4.01	7.63	1.11	1.44	0.57
B-2	含油砂岩	②混合溶剂+超声波抽提	16.85	2.43	-	1.44	0.46
B-3	含油砂岩	③混合溶剂+超声波抽提	12.71	3.23	-	1.36	0.46
B-4	含油砂岩	④正己烷+超声波抽提	14.02	51.62	-	1.02	0.57
B-5	含油砂岩	⑤正己烷+超声波抽提	10.24	36.31	-	1.10	0.56
注：MC.甲基咔唑；DMC.二甲基咔唑，表中混合溶剂为二氯甲烷∶甲醇(9∶1，体积比)；[a]/[c].苯并咔唑[a]/[c]。

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表 4 鄂尔多斯盆地陕北斜坡X、Y地区含油砂岩抽提物地球化学数据

Table 4. Geochemical data of oil-bearing sandstone extracts from X and Y areas of Shaanbei Slope, Ordos Basin

井名	Pr/nC₁₇	Ph/nC₁₈	Pr/Ph	伽马蜡烷指数	C₂₇/C₂₉规则甾烷	C₂₉20S/(S+R)	C₂₉ββ/(ββ+αα)	Ts/(Ts+Tm)	C₂₉Ts/C₃₀藿烷	重排藿烷指数
X1	0.51	0.55	0.80	0.07	1.16	0.47	0.53	0.44	0.15	0.06
X2	0.48	0.49	0.78	0.06	1.36	0.44	0.52	0.49	0.16	0.07
X3	0.53	0.54	0.76	0.07	1.19	0.44	0.53	0.46	0.16	0.07
X4	0.50	0.55	0.66	0.07	1.10	0.44	0.53	0.43	0.15	0.05
Y1	0.49	0.62	0.55	0.06	1.26	0.45	0.52	0.37	0.13	0.03
Y2	0.49	0.55	0.63	0.07	1.06	0.48	0.53	0.35	0.14	0.03

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