单质硫和含硫矿物对固体沥青中芳烃化合物热演化过程的影响

张延延; 李水福; 胡守志; 方新焰; 吴亮亮

doi:10.11781/sysydz2021061064

单质硫和含硫矿物对固体沥青中芳烃化合物热演化过程的影响

doi: 10.11781/sysydz2021061064

张延延^{1, 2,},
李水福¹,
胡守志¹,
方新焰²,
吴亮亮^2, ,

1.
中国地质大学(武汉), 武汉 430074
2.
中国科学院广州地球化学研究所有机地球化学国家重点实验室, 广州 510640

基金项目:

“十三五”国家科技重大专项 2017ZX05008-002

国家自然科学基金面上项目 41673044

国家自然科学基金面上项目 42073067

中国科学院战略性先导科技专项（B类） XDB10010502

详细信息

作者简介:
张延延(1995-), 男, 博士研究生, 从事有机与油气地球化学研究。E-mail: here.yan@qq.com

通讯作者:
吴亮亮(1986-), 男, 博士, 副研究员, 从事有机与油气地球化学研究。E-mail: wuliangliang@gig.ac.cn

中图分类号: TE122.113
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出版历程
- 收稿日期: 2020-12-03
- 修回日期: 2021-09-22
- 刊出日期: 2021-11-28

Effects of elemental sulfur and sulfur-bearing minerals on the thermal evolution of aromatic compounds in solid bitumen

1.
China University of Geosciences (Wuhan), Wuhan, Hubei 430074, China
2.
State Key Laboratory of Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China

摘要

摘要: 前人研究表明，部分芳烃化合物比值参数与有机质成熟度具有良好的线性关系。为了明确常用芳烃化合物比值参数在不同含硫地质条件下的适用性，通过对四川盆地低熟固体沥青样品开展在单质硫和含硫矿物（黄铁矿、硫酸亚铁、硫酸铁和硫酸钙）存在条件下的加水热模拟实验，进而探讨上述含硫物质在固体沥青热演化过程中对其中所赋存的芳烃化合物的影响。研究表明：各类含硫物质均不同程度影响了芳烃化合物甲基化、甲基重排及去甲基化的进程和强度，随之改变了常用芳烃化合物比值参数的适用性及适用范围。但也存在一些在含硫环境下仍能稳定表征有机质成熟度的参数，如萘系化合物的1，2，3-TMN/2，3，6-TMN、菲系化合物的P/（P+∑MP）和甲基菲指数MPI、二苯并噻吩系化合物的4，6-DMDBT/3，6-DMDBT等参数，能够应用于含硫地质体中有机质成熟度的表征。
- 单质硫 /
- 含硫矿物 /
- 芳烃化合物 /
- 成熟度参数 /
- 热模拟实验 /
- 固体沥青 /
- 四川盆地
Abstract: Previous studies have shown that some of the aromatic compound parameters have good correlation with the maturity of organic matter. However, it is still unknown whether the widely used aromatic maturity-related parameters are available with the co-existence of sulfur (elemental and/or sulfur-bearing minerals). Artificial simulation experiments of solid bitumen together with elemental sulfur and/or sulfur-bearing minerals (e.g., pyrite, ferrous sulfate, iron sulfate, and calcium sulfate) were carried out to investigate the influence of elemental sulfur and sulfur-bearing minerals on the thermal evolution of aromatic compounds. Results illustrated that some reactions including methylation, alkyl rearrangement and demethylation of aromatic compounds were affected with various extents by the existence of elemental sulfur and sulfur-bearing minerals. Thus, the applicability of the aromatic index should be careful. This study also found some parameters that still can effectively evaluate the maturity of organic matter in the sulfur-bearing environment, such as 1,2,3-TMN/2,3,6-TMN, P/(P+∑MP), MPI and 4,6-DMDBT/3,6-DMDBT.
- elemental sulfur /
- sulfur-bearing minerals /
- aromatic compound /
- maturity parameter /
- thermal simulation experiment /
- solid bitumen /
- Sichuan Basin

HTML全文

图 1 龙门山北段构造—地层区域分布及采样位置示意

据参考文献[40]修改。

Figure 1. Tectonic-stratigraphic belts and sampling wells in the northern section of Longmen Mountain

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图 2 原始样品芳烃GC-MS谱图

Figure 2. GC-MS spectrum of aromatic compounds in solid bitumen samples

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图 3 各系列样品GC-MS的TIC谱图

Figure 3. TIC spectra of GC-MS in different samples

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图 4 各系列样品中萘系化合物GC-MS谱图

a为未知物；1为2-甲基萘；2为1-甲基萘；3为2-乙基萘；4为1-乙基萘；5为2,6+2,7-二甲基萘；6为1,3+1,7-二甲基萘；7为1,6-二甲基萘；8为1,4+2,3-二甲基萘；9为1,5-二甲基萘；10为1,2-二甲基萘；11为1,3,7-三甲基萘；12为1,3,6-三甲基萘；13为1,3,5+1,4,6-三甲基萘；14为2,3,6-三甲基萘；15为1,2,7+1,6,7+2,3,5-三甲基萘；16为1,2,3-三甲基萘

Figure 4. GC-MS spectra of naphthalene compounds in different samples

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图 5 各系列样品中MN、DMN和TMN的相对丰度

Figure 5. Relative abundance of MN, DMN and TMN in different samples

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图 6 各系列样品中萘系化合物常用比值柱状图及与R_o关系的折线图

DNR=[2(β), 6(β)-二甲基萘+2(β), 7(β)-二甲基萘]/1(α), 5(α)-二甲基萘；TNR₂=[1(α), 3(β), 7(β)-三甲基萘+ 2(β), 3(β), 6(β)-三甲基萘]/[1(α), 3(β), 5(α)-三甲基萘+1(α), 3(β), 6(β)-三甲基萘+1(α), 4(α), 6(β)-三甲基萘]

Figure 6. Histograms of common ratios of naphthalene compounds in different samples and line graphs of the relationship with R_o

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图 7 各系列样品中菲系化合物GC-MS谱图

17为菲；18为3-甲基菲；19为2-甲基菲；20为9-甲基菲；21为1-甲基菲；22为3,5+2,6二甲基菲；23为2,7二甲基菲；24为1,3+3,9+2,10+3,10-二甲基菲；25为1,6+2,9+2,5二甲基菲；26为1,7-二甲基菲；27为2,3+1,9+4, 9+4,10-二甲基菲；28为1,8-二甲基菲；29为1,2-二甲基

Figure 7. GC-MS spectra of phenanthrene compounds in different samples

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图 8 各系列样品中菲系化合物常用比值柱状图及与R_o关系折线图

MPR=[2(β)-MP+3(β)-MP]/[1(α)-MP+9(α)-MP]；MPI=1.5(2-MP+3-MP)/(P+1-MP+9-MP)

Figure 8. Histograms of common ratios of phenanthrene compounds in different samples and line graphs of the relationship with R_o

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图 9 各系列样品中二苯并噻吩系列化合物GC-MS谱图

DBT为二苯并噻吩；MDBT为甲基二苯并噻吩；DMDBT为二甲基二苯并噻吩
b为未知物；30为二苯并噻吩；31为4-甲基二苯并噻吩；32为2,3-甲基二苯并噻吩；33为1-甲基二苯并噻吩；34为4-乙基二苯并噻吩；35为4,6-二甲基二苯并噻吩；36为2,4-二甲基二苯并噻吩；37为2,6-二甲基二苯并噻吩；38为3,6-二甲基二苯并噻吩；39为2,5-二甲基二苯并噻吩；40为2,7+3,7-二甲基二苯并噻吩；41为1,4-二甲基二苯并噻吩；42为1,3+3,4-二甲基二苯并噻吩；43为1,7-二甲基二苯并噻吩

Figure 9. GC-MS spectra of dibenzothiophene compounds in different samples

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图 10 各系列样品中二苯并噻吩系化合物常用比值柱状图和与R_o关系折线图

MDR=4-MDBT/1-MDBT

Figure 10. Histograms of common ratios of dibenzothiophene compounds in different samples and line graphs of the relationship with R_o

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图 11 各系列样品中三芳甾类化合物GC-MS谱图

44为C₂₀-三芳甾烷(1TA20)；45为C₂₀-甲基三芳甾烷(2TA21)；46为C₂₆-三芳甾烷(20S)(3TA26)；47为C₂₆-三芳甾烷(20R)+C₂₇-三芳甾烷(20S)(4TA26+A27)；48为C₂₈-三芳甾烷(20S)(5TA28)；49为C₂₇-三芳甾烷(20R)(6TA27)；50为C₂₈-三芳甾烷(20R)(7TA28)

Figure 11. GC-MS spectra of triaromatic steroids in different samples

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图 12 部分系列样品中三芳甾类化合物相对丰度折线图

图中横坐标化合物代号名称见图 11中的图注。

Figure 12. Triaromatic steroids histogram in some series of samples

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表 1 玻璃管热模拟实验条件

Table 1. Experimental conditions for glass tube thermal simulations

温度/℃	编号	固体沥青/mg	H₂O/mg	添加剂/mg
温度/℃	编号	固体沥青/mg	H₂O/mg	CaSO₄	FeS₂	FeSO₄	Fe₂(SO₄)₃	S
300	300-1	96.0	24.0
	300-2	98.9	24.0	21.0
	300-3	100.3	24.2		20.8
	300-4	101.6	24.1			21.0
	300-5	103.4	23.9				21.3
	300-6	102.6	24.6					20.5
330	330-1	99.0	23.7
	330-2	101.6	23.5	20.9
	330-3	101.1	23.6		19.4
	330-4	100.9	23.2			19.8
	330-5	102.1	23.9				21.1
	330-6	99.8	23.3					21.4
350	350-1	94.6	23.5
	350-2	99.9	25.3	20.8
	350-3	98.3	24.1		20.3
	350-4	101.4	23.7			20.6
	350-5	99.6	23.7				20.9
	350-6	102.9	23.9					21.0
370	370-1	101.8	23.8
	370-2	103.0	24.5	20.0
	370-3	101.5	23.8		20.9
	370-4	101.3	24.0			22.6
	370-5	103.6	23.6				21.4
	370-6	100.7	24.5					19.7

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