Differences in hydrocarbon composition of shale oils in different phase states from the Qingshankou Formation, Songliao Basin, as determined from fluorescence experiments

doi:10.1007/s11707-021-0915-8

Front. Earth Sci.

2021, Vol. 15

Issue (2) : 438-456 https://doi.org/10.1007/s11707-021-0915-8

RESEARCH ARTICLE

Differences in hydrocarbon composition of shale oils in different phase states from the Qingshankou Formation, Songliao Basin, as determined from fluorescence experiments

Longhui BAI¹, Bo LIU^2,¹(

), Jianguo YANG³, Shansi TIAN¹, Boyang WANG¹, Saipeng HUANG¹

¹. Accumulation and Development of Unconventional Oil and Gas, State Key Laboratory Cultivation Base, Northeast Petroleum University, Daqing 163318, China
². Hubei Key Laboratory of Petroleum Geochemistry and Environment, Yangtze University, Wuhan 430100, China
³. Shenyang Center, China Geological Survey, Shenyang 110034, China

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Abstract

The phase state of shale oil has a significant impact on its mobility. The mineral and organic matter in shale reservoirs play an important role in oil phase. This study attempts to evaluate the properties of shale oils in different phase states and to investigate how these differences are related to initial shale composition. Samples from the first member of the Qingshankou (Q1) Formation were analyzed using X-ray diffraction, total organic carbon content, rock pyrolysis solvent extraction and group component separation. Subsequently, fluorescence techniques were used to quantitatively determine the content and properties of the free oil (FO), the adsorbed oil associated with carbonate (ACO), and the adsorbed oil associated with silicate and clay-organic complexes (AKO). The results showed that non-hydrocarbons and asphaltenes are the primary fluorescing compounds on shale grain. FO is the dominant phase in the Q1 Formation. The quantitative grain fluorescence on extraction (QGF-E) and total scanning fluorescence (TSF) spectra of ACO and AKO show a significant redshift compared to the FO. The TSF spectra of FO have a characteristic skew to the left and a single peak distribution, suggesting a relatively light hydrocarbon component. The TSF spectra of ACO show a skew to the right and an even, double-peaked distribution. The TSF spectra of AKO show a single peak with a skew to the right, indicating that ACO and AKO hydrocarbons are heavier than FO hydrocarbons. In summary, enrichment of carbonate minerals in shale may result in mis-identification of “sweet spots” when using QGF. The normalized fluorescence intensity of QGF-E and TSF are effective indexes allowing oil content evaluation. As an additional complicating factor, hydrocarbon fractionation occurs during generation and expulsion, leading to a differentiation of oil composition. And FO has high relatively light hydrocarbon content and the strongest fluidity.

Keywords stepwise extraction fluorescence spectroscopic techniques shale grain shale oil phase

Corresponding Author(s): Bo LIU

Online First Date: 09 October 2021 Issue Date: 26 October 2021

Cite this article:

Longhui BAI,Bo LIU,Jianguo YANG, et al. Differences in hydrocarbon composition of shale oils in different phase states from the Qingshankou Formation, Songliao Basin, as determined from fluorescence experiments[J]. Front. Earth Sci., 2021, 15(2): 438-456.

URL:

https://academic.hep.com.cn/fesci/EN/10.1007/s11707-021-0915-8
https://academic.hep.com.cn/fesci/EN/Y2021/V15/I2/438

Fig.1 (a) Tectonic Unit Division, (b) Studied Area and Location of well J. (Modified from Liu et al., 2019a).

Fig.2 Flow chart of the whole experimental procedure.

Fig.3 (a) Plot of T_max versus HI. (b) Correlation between S₂ and TOC. (c) Plot of S₁ and TOC.

Fig.4 (a) Triangular plot of rock mineral composition of the Q1 Formation. (b) Bar graph of clay mineral content of the Q1 Formation.

Tab.1 Bulk geochemical parameters and XRD results of the shale samples of the Q1 Formation

Fig.5 Percentage content of group components of EOM.

Tab.2 Group compounds separation results of the shale samples of the Q1 Formation

Fig.6 QGF spectrum of the shale grains of the Q1 Formation.

Tab.3 QGF results of the continental shale grains of the Q1 Formation.

Tab.4 QGF-E and TSF results of shale oils in different phase states

Fig.7 QGF-E spectrum of shale oils in different phase states.

Fig.8 TSF spectrum of shale oils in different phase states.

Fig.9 (a) Correlation between QGF intensity and the sum of non-hydrocarbon and asphaltene. (b) Correlation between QGF intensity and the sum of saturated and aromatic hydrocarbon. (c) Correlation between Carbonate minerals content and the sum of non-hydrocarbon and asphaltene. (d) Correlation between Carbonate minerals content and the sum of saturated and aromatic hydrocarbon.

Fig.10 (a) Correlations between the normalized FO QGF-E intensity and S₁, EOM respectively. (b) Correlation between the normalized FO QGF-E intensity and normalized TSF intensity of FO. (c) Correlation between the normalized ACO QGF-E intensity and Carbonate minerals. (d) Correlation between the normalized ACO QGF-E intensity and TOC. (e) Correlation between the normalized AKO QGF-E intensity and TOC. (f) TSF R₁ distribution of shale oil in different phase states.

Fig.11 (a) Cross plot of QGF-E spectrum of shale oils in different phase states. (b) Cross plot of TSF spectrum of shale oils in different phase states.

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