Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection

The investigation of low-temperature oxidation (LTO) of crude oil within tight shale holds significant importance due to its implications for subsequent oxidation reactions and enhanced oil recovery in the process of air injection. In this study, the tight shale sample underwent oxidation at various...

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Main Authors: Shuai Zhao, Wanfen Pu, Yibo Li, Qi Jiang
Format: Article
Language:English
Published: KeAi Communications Co., Ltd. 2025-02-01
Series:Petroleum
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Online Access:http://www.sciencedirect.com/science/article/pii/S2405656123000809
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author Shuai Zhao
Wanfen Pu
Yibo Li
Qi Jiang
author_facet Shuai Zhao
Wanfen Pu
Yibo Li
Qi Jiang
author_sort Shuai Zhao
collection DOAJ
description The investigation of low-temperature oxidation (LTO) of crude oil within tight shale holds significant importance due to its implications for subsequent oxidation reactions and enhanced oil recovery in the process of air injection. In this study, the tight shale sample underwent oxidation at various LTO temperatures, followed by an analysis of the resulting gas composition. Furthermore, the oxidized oil was separated from the tight shale and subjected to characterization using electron paramagnetic resonance, nuclear magnetic resonance, and negative ion electrospray Fourier transform-ion cyclotron resonance mass spectrometry techniques. The primary focus was on examining the distinct LTO reaction pathways observable across different temperature ranges. The findings demonstrated a correlation between LTO temperature and the concentration of free radicals, which predominantly resided on aromatic hydrocarbons, alkanes, and oxygen atoms. Additionally, the proton count of polycyclic aromatic hydrocarbons exhibited a continuous increase from 83 to 350°C, suggesting intensified aromatization and condensation reactions involving aliphatic and aromatic compounds. With rising LTO temperature, the molecular structure of O2 compounds underwent significant transformations, characterized by increased condensation degree and a decrease in low carbon number molecular structures, while higher equivalent double bonds and carbon number molecular structures became more prevalent. The LTO reaction pathways of shale oil included cycle paths 1, 2, and 3. The influence of cycle path 1 diminished at temperatures ranging from 83 to 150°C and 250 to 350°C, whereas the significance of cycle paths 2 and 3 increased, resulting in an overall escalation of the oxidation rate with temperature elevation. It was observed that the shale oil LTO process exhibited a negative temperature coefficient within the temperature range of 150 to 250°C, emphasizing the criticality of overcoming the energy barrier in this region to achieve stable combustion. This comprehensive investigation provides valuable insights into the mechanisms underlying LTO in crude oil confined within tight shale.
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spelling doaj-art-fe32fe1c2d7b48cdbdca36d16d9cee852025-08-20T03:15:28ZengKeAi Communications Co., Ltd.Petroleum2405-65612025-02-01111849310.1016/j.petlm.2023.12.005Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injectionShuai Zhao0Wanfen Pu1Yibo Li2Qi Jiang3State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China; Tianfu Yongxing Laboratory, Chengdu, 610213, China; Corresponding author.State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, ChinaState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China; Corresponding author.State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, ChinaThe investigation of low-temperature oxidation (LTO) of crude oil within tight shale holds significant importance due to its implications for subsequent oxidation reactions and enhanced oil recovery in the process of air injection. In this study, the tight shale sample underwent oxidation at various LTO temperatures, followed by an analysis of the resulting gas composition. Furthermore, the oxidized oil was separated from the tight shale and subjected to characterization using electron paramagnetic resonance, nuclear magnetic resonance, and negative ion electrospray Fourier transform-ion cyclotron resonance mass spectrometry techniques. The primary focus was on examining the distinct LTO reaction pathways observable across different temperature ranges. The findings demonstrated a correlation between LTO temperature and the concentration of free radicals, which predominantly resided on aromatic hydrocarbons, alkanes, and oxygen atoms. Additionally, the proton count of polycyclic aromatic hydrocarbons exhibited a continuous increase from 83 to 350°C, suggesting intensified aromatization and condensation reactions involving aliphatic and aromatic compounds. With rising LTO temperature, the molecular structure of O2 compounds underwent significant transformations, characterized by increased condensation degree and a decrease in low carbon number molecular structures, while higher equivalent double bonds and carbon number molecular structures became more prevalent. The LTO reaction pathways of shale oil included cycle paths 1, 2, and 3. The influence of cycle path 1 diminished at temperatures ranging from 83 to 150°C and 250 to 350°C, whereas the significance of cycle paths 2 and 3 increased, resulting in an overall escalation of the oxidation rate with temperature elevation. It was observed that the shale oil LTO process exhibited a negative temperature coefficient within the temperature range of 150 to 250°C, emphasizing the criticality of overcoming the energy barrier in this region to achieve stable combustion. This comprehensive investigation provides valuable insights into the mechanisms underlying LTO in crude oil confined within tight shale.http://www.sciencedirect.com/science/article/pii/S2405656123000809Low-temperature oxidationShale oilAir injectionElectron paramagnetic resonance
spellingShingle Shuai Zhao
Wanfen Pu
Yibo Li
Qi Jiang
Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
Petroleum
Low-temperature oxidation
Shale oil
Air injection
Electron paramagnetic resonance
title Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
title_full Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
title_fullStr Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
title_full_unstemmed Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
title_short Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
title_sort low temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection
topic Low-temperature oxidation
Shale oil
Air injection
Electron paramagnetic resonance
url http://www.sciencedirect.com/science/article/pii/S2405656123000809
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AT wanfenpu lowtemperatureoxidationcharacteristicsandreactionpathwaysofcrudeoilwithintightshaleduringairinjection
AT yiboli lowtemperatureoxidationcharacteristicsandreactionpathwaysofcrudeoilwithintightshaleduringairinjection
AT qijiang lowtemperatureoxidationcharacteristicsandreactionpathwaysofcrudeoilwithintightshaleduringairinjection