一种解释高-过成熟烷烃气碳同位素系列倒转的新观点：芳香烃脱甲基作用

彭威龙; 刘全有; 胡国艺; 吕玥; 孟庆强; 郭丰涛; 关海洋

doi:10.3799/dqkx.2019.133

一种解释高-过成熟烷烃气碳同位素系列倒转的新观点：芳香烃脱甲基作用

doi: 10.3799/dqkx.2019.133

彭威龙^{1, 2, 3, ,},
刘全有²,
胡国艺³,
吕玥³,
孟庆强²,
郭丰涛²,
关海洋⁴

1.
页岩油气富集机理与有效开发国家重点实验室, 北京 100083
2.
中国石化石油勘探开发研究院, 北京 100083
3.
中国石油勘探开发研究院, 北京 100083
4.
中国石油辽河油田分公司勘探开发研究院, 辽宁盘锦 124010

基金项目:

中国博士后科学基金项目 2019M650967

国家自然科学基金项目 41902160

国家自然科学基金项目 41625009

国家重大科技专项 2016ZX05007-001

国家重点研发计划 2017YFC0603102

中国科学院A类战略先导科技专项 XDA14010404

详细信息

作者简介:
彭威龙(1988-), 男, 博士后, 主要从事热模拟实验, 天然气地质和天然气地球化学方面的研究

中图分类号: P618.13
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出版历程
- 收稿日期: 2019-06-04
- 刊出日期: 2020-04-15

A New Interpretation of Carbon Isotope Series Reverse of Highly-Over Mature Alkane Gases: Demethylation of Aromatic Hydrocarbons

1.
State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, SINOPEC, Beijing 100083, China
2.
Petroleum Exploration and Production Research Institute, SINOPEC, Beijing 100083, China
3.
Research Institute of Petroleum Exploration & Development, PetroChina, Beijing 100083, China
4.
Exploration and Development Research Institute of Liaohe Oilfield Company, CNPC, Panjin 124010, China

摘要

摘要: 天然气成因机理复杂，鉴于在高-过成熟阶段烷烃气碳同位素系列倒转普遍存在，而高-过成熟阶段有机质中常富含芳环结构，利用芳香烃（甲苯）热裂解实验探讨高-过成熟阶段烷烃气碳同位素系列倒转成因.甲苯热裂解实验表明随着模拟温度的增加，烷烃气产率逐渐增大；模拟产物中H₂产率也随着模拟温度的增加而增加.甲苯裂解产物中δ¹³C₁、δ¹³C₂和δ¹³C₃分布区间分别为-31.8‰~-27.7‰，-31.0‰~-20.4‰和-31.0‰~-20.4‰.在甲苯热模拟实验450℃时，出现了烷烃气碳同位素系列的部分倒转（δ¹³C₁>δ¹³C₂ < δ¹³C₃）.发现无论是煤成气还是油型气，在高-过成熟阶段都会出现烷烃气碳同位素系列的倒转，结合本次模拟实验结果，认为芳香烃脱甲基作用可能是烷烃气高-过成熟阶段出现碳同位素系列倒转的一个重要原因.
- 热模拟实验 /
- 天然气 /
- 碳同位素 /
- 芳香烃裂解 /
- 甲苯 /
- 烃
Abstract: The genetic mechanism of natural gas is complex. In view of the fact that carbon isotope series reverse of alkane gas exists generally in the highly-over mature stage, and the organic matter in the highly-over mature stage is often rich in aromatic ring structure, the carbon isotope series reverse of alkane gas in the highly-over mature stage is discussed by means of pyrolysis experiments of aromatic hydrocarbons (toluene). The pyrolysis of toluene shows that the yield of alkane gas increases with the increase of simulated temperature, and the yield of H₂ in the product increases with the increase of simulated temperature. The distribution ranges of δ¹³C₁, δ¹³C₂ and δ¹³C₃ in toluene pyrolysis products are -31.8‰ to -27.7‰, -31.0‰ to -20.4‰ and -31.0‰ to -20.4‰, respectively. In the toluene thermal simulation experiment at 450℃, partial reversal of carbon isotope series of alkanes occurred (δ¹³C₁>δ¹³C₂ < δ¹³C₃). It is found that carbon isotope series reversal occurs in both coal type gas and oil type gas at highly-over mature stage. Combining with the simulation results, it is considered that aromatic hydrocarbon demethylation may be an important reason for carbon isotope series reversal in highly-over mature stage of alkane gas.
- thermal simulation experiment /
- natural gas /
- carbon isotope /
- aromatic hydrocarbon pyrolysis /
- toluene /
- hydrocarbons

HTML全文

图 1 甲苯裂解产物产率特征(a)、相对含量特征(b)和烷烃气碳同位素连线(c)

Fig. 1. Yield characteristics (a), relative content characteristics (b) and carbon isotope series of alkane gas (c) of toluene pyrolysis products

下载: 全尺寸图片幻灯片

图 2 煤成气δ¹³C₂-δ¹³C₁和δ¹³C₁相关图(a)和页岩气δ¹³C₂-δ¹³C₁和δ¹³C₁相关图(b)

Fig. 2. δ¹³C₂-δ¹³C₁ vs. δ¹³C₁ of coal type gas (a); δ¹³C₂-δ¹³C₁ vs. δ¹³C₁ of shale gas (b)

下载: 全尺寸图片幻灯片

图 3 芳香族化合物脱甲基形成CH₄示意图

Fig. 3. Demethylation of aromatic compounds to form CH₄

下载: 全尺寸图片幻灯片

表 1 甲苯裂解主要产物产率特征

Table 1. Yield characteristics of main products from toluene pyrolysis

温度(℃)	样品量(mg)	主要组分产率(mL/g)						烃类气产率(mL/g)
温度(℃)	样品量(mg)	CH₄	C₂H₆	C₃H₈	iC₄	nC₄	H₂	烃类气产率(mL/g)
450	72.9	13.23	0.25	0.07	0.01	0.01	1.16	13.56
475	69.7	55.12	0.70	0.18	0.01	n.d.	1.36	56.02
500	61.1	193.99	6.19	0.99	0.04	n.d.	3.61	201.22
525	60.2	260.85	11.23	0.60	0.02	n.d.	5.08	272.70
550	52.9	294.55	8.48	0.18	n.d.	n.d.	6.26	303.21
注:"n.d."表示没有检测到数据, 下同.

下载: 导出CSV

表 2 甲苯裂解主要产物相对含量及碳同位素组成

Table 2. Relative content and carbon isotope composition of main products from toluene pyrolysis

温度(℃)	主要化学组成(%)						C₁/C_1-4	δ¹³C(‰, VPDB)
温度(℃)	CH₄	C₂H₆	C₃H₈	iC₄	nC₄	H₂	C₁/C_1-4	C₁	C₂	C₃
450	12.42	0.24	0.06	0.01	0.01	1.09	0.975	-27.7	-28.1	-23.5
475	64.61	0.82	0.21	0.02	n.d.	1.59	0.984	-31.8	-31.0	-23.1
500	89.34	2.85	0.46	0.02	n.d.	1.66	0.964	-30.5	-28.8	-19.3
525	91.17	3.93	0.21	0.01	n.d.	1.78	0.957	-29.9	-24.4	-15.1
550	91.37	2.63	0.06	n.d.	n.d.	1.94	0.971	-29.5	-20.4	-16.9

下载: 导出CSV

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