Thermal cracking, aquathermolysis, and their upgrading effects of Mackay River oil sand

Qu, Xiao; Li, Yang; Li, Songyan; Wang, Jiqian; Xu, Hai; Li, Zhaomin

doi:10.1016/j.petrol.2021.108473

Cited by 31 publications

(22 citation statements)

References 19 publications

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“…This behavior could be observed in all of the cases evaluated where there was a reduction in viscosity of up to 13% additional regarding the tests without its presence, as shown in Figure . This test allowed us to confirm the hypotheses proposed by several authors, ,,− which concluded that the presence of clay minerals can lead to an additional decrease in this physical property, as was shown for the 70% sand scenarios where the higher clay content was added. The results show that the effect of metal ions from iron naphthenate on the viscosity of the enhanced base crude is also beneficial.…”

Section: Resultssupporting

confidence: 81%

Effect of Mineralogy on the Physicochemical Properties of a Heavy Crude Oil in Hybrid Steam Injection Technologies Using 1H NMR

et al. 2022

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The present study focused on the experimental evaluation of the effect of mineralogy in oil upgrading under two hybrid steam injection technologies. The tests were carried out in a batch reactor, using iron naphthenate as the catalyst and flue gas. The physical changes of the crude were evaluated by density and viscosity measurements, while the variations of the crude molecular structure were quantified using nuclear magnetic resonance (1H NMR) spectroscopy. The results showed that for the technique with catalyst, the scenario with the highest proportion of clay increased the API gravity by 27% and reduced the crude viscosity by 39%. The additional upgrading was the result of mineral presence with a contribution of 13% due to H2 production and the inhibition of polymerization. Additionally, the presence of the mineral phase with flue gas in the system reverses some of the subprocesses of the aquathermolysis reactions that favor the improvement of the crude. For this hybrid technique, the best scenario was achieved in the absence of the mineral phase with an increase of 10% in API gravity and a reduction of 41% in viscosity concerning the base crude as a product of the flue gas mechanisms. The changes in the physical properties can be correlated with the modifications in the chemical structure of the crude oil. These changes were a result of dealkylation, hydrogenation, and condensation reactions, evidenced by the variation of average molecular parameters, obtained by 1H NMR, such as the aromaticity factor and the number of substituted rings.

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Section: Resultssupporting

confidence: 81%

Effect of Mineralogy on the Physicochemical Properties of a Heavy Crude Oil in Hybrid Steam Injection Technologies Using 1H NMR

et al. 2022

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“…In the previous work, thermal conversion of bitumen at 250 °C in the presence of solids alone increased the viscosity of bitumen by about 5 times its original viscosity, accompanied by an increase in the free radical concentration of bitumen . On the other hand, when the bitumen was treated on its own, these changes were not observed. ,, Generally, heavier fractions of bitumen have a high viscosity and also contain more free radicals. − It is therefore hypothesized that minerals promote the formation of heavier material in bitumen at 250 °C, which would be consistent with the increase in the measured viscosity and free radical content of the product.…”

Section: Introductionmentioning

confidence: 67%

“…3 On the other hand, when the bitumen was treated on its own, these changes were not observed. 3,7,8 Generally, heavier fractions of bitumen have a high viscosity and also contain more free radicals. 9−12 It is therefore hypothesized that minerals promote the formation of heavier material in bitumen at 250 °C, which would be consistent with the increase in the measured viscosity and free radical content of the product.…”

Section: Introductionmentioning

confidence: 99%

Free Radical and Cationic Addition due to Clay Minerals Found in Bitumen Froth at 250 °C Probed with Use of α-Methylstyrene and 1-Octene

Turuga

Klerk

2022

Energy Fuels

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Following previous evidence that hydrothermal treatment of bitumen froth does not lead to bitumen upgrading at 250 °C and promotes viscosity increase, the current study explores the free radical and cationic reactivity of clay minerals found in bitumen froth in promoting heavier material formation through addition reactions. The current investigation employed α-methylstyrene (AMS) and 1-octene as probe molecules instead of bitumen froth, and their conversion at 250 °C in the presence of clay minerals kaolinite and illite was studied in batch reactors. Thermal conversion of AMS and 1-octene at 250 °C in the absence of minerals was observed to be low. In the presence of clay minerals, not only the conversion of AMS and 1-octene was increased but also reactions such as dimerization of AMS and alkylation of 1-octene and toluene (used as solvents) were mainly promoted, leading to heavier product formation. Double-bond isomerization of 1-octene and cumene formation from AMS was side reactions that were also promoted by the clay minerals. Suppression of mineral-related conversion by pyridine and selectivity to different reaction products that enabled differentiation between free radical and cationic reaction pathways indicated that the mineral-related conversion was predominantly cationic in nature. Using the reactions in the presence of minerals and pyridine as surrogates for alkaline bitumen froth, it was concluded that even under alkaline conditions, minerals could promote heavier material formation through cationic addition.

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“…Extra-heavy crude oils and bitumens feature high viscosity (>10 000 cPs) and high density (>1.0 g/mL) or low API gravity (<10.0), which is usually attributed to their high content of heteroatoms (O, N, S, V, and Ni) and increased asphaltene concentration compared to light and medium oils. , Therefore, petroleum companies usually perform in situ upgrading to improve the mobility of extra-heavy fossil fuels . Generally, the goal of upgrading extra-heavy oils, via methods such as visbreaking and hydroconversion, is viscosity reduction, via cracking reactions to decrease molecular weight and/or disruption of intermolecular interactions that likely promote strong aggregation among specific petroleum fractions (e.g., asphaltenes). − Therefore, it is likely that viscosity reduction upon upgrading results from a decrease in the concentration of asphaltenes and resins, known for their higher heteroatom content and stronger aggregation tendencies. Viscosity improvement also arises from increasing the content of saturates and aromatics, with a concurrent decrease of the concentration of sulfur and other molecular features such as aromaticity. , …”

Section: Introductionmentioning

confidence: 99%

Molecular Characterization of Remnant Polarizable Asphaltene Fractions Upon Bitumen Upgrading and Possible Implications in Petroleum Viscosity

et al. 2022

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Thermal processing and hydrotreatment are used to decrease the viscosity of Alberta bitumen. However, changes in bulk properties, such as API gravity and viscosity, do not correlate to the gravimetric content of maltenes and asphaltenes. Thus, the work herein employs an extrography separation that yields asphaltene fractions enriched with distinct structural motifs and aggregation tendencies to investigate if changes in viscosity could be linked to the transformation or survival of specific asphaltene compounds and/or extrography fractions. Samples with limited change in viscosity upon thermal processing display minor changes in the gravimetric distribution of the extrography fractions, specifically polarizable species (Tol/THF/MeOH fraction). Ultrahigh-resolution mass spectrometry analysis demonstrates that such samples reveal neither a significant decrease in chemical polydispersity nor a change in the relative content of multicore/archipelago structural motifs post thermal treatment. Conversely, hydroprocessed samples with a pronounced viscosity reduction feature a remarkably lower chemical polydispersity and increased content of single-core (island) structural motifs. Polarizable asphaltene fractions from severely hydrotreated samples feature S-containing species with a low aromaticity, which on the basis of their molecular composition suggests that they are composed of the expected, alkyl substituted, geologically stable thiophenic cores (e.g., benzothiophene) as well as “unexpected” sulfides and sulfoxides. Collectively, the results suggest that the high viscosity of thermally upgraded samples could be correlated to the survival of asphaltene species with high heteroatom content (up to five heteroatoms per molecule) and persistent, high abundance of archipelago structural motifs. Thus, it is suspected that nanoaggregation of such fractions prevents their transformation into lighter products.

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Thermal cracking, aquathermolysis, and their upgrading effects of Mackay River oil sand

Cited by 31 publications

References 19 publications

Effect of Mineralogy on the Physicochemical Properties of a Heavy Crude Oil in Hybrid Steam Injection Technologies Using 1H NMR

Effect of Mineralogy on the Physicochemical Properties of a Heavy Crude Oil in Hybrid Steam Injection Technologies Using 1H NMR

Free Radical and Cationic Addition due to Clay Minerals Found in Bitumen Froth at 250 °C Probed with Use of α-Methylstyrene and 1-Octene

Molecular Characterization of Remnant Polarizable Asphaltene Fractions Upon Bitumen Upgrading and Possible Implications in Petroleum Viscosity

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