Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part III – changes in composition resins and asphaltenes

Vakhin, Аlexey V.; Ситнов, С. А.; Mukhamatdinov, Irek I.; Aliev, Firdavs A.; Kudryashov, S. I.; Afanasiev, Igor S.; Petrashov, Oleg V.; Varfolomeev, Mikhail A.; Нургалиев, Д. К.

doi:10.1080/10916466.2018.1514413

Cited by 37 publications

(11 citation statements)

References 19 publications

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“…After 12 h thermo-catalytic upgrading, the content of resins and asphaltenes were reduced by 27% and 40%, respectively (Table 1) [19,20]. The increase in the light fractions of oil is due to the breakage of such high-molecular hydrocarbons.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Aquathermolysis of Boca de Jaruco Heavy Oil with Nickel-Based Oil-Soluble Catalyst

et al. 2020

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This paper investigates aquathermolysis of heavy oil in carbonate reservoir rocks from Boca de Jaruco, which is developed by the cyclic steam stimulation method. The nickel-based catalyst precursor was introduced in order to intensify the conversion processes of heavy oil components. The active form of such catalysts—nickel sulfides—are achieved after steam treatment of crude oil at reservoir conditions. The experiments were carried out on a rock sample extracted from the depth of 1900 m. Changes in composition and structure of heavy oil after the conversion were identified using SARA-analysis, Gas Chromatography-Mass Spectroscopy of saturated fractions, FTIR spectroscopy of saturated fractions, and MALDI of resins. It is revealed that catalyst particles provide a reduction in the content of resins and asphaltenes due to the destruction of carbon-heteroatom bonds. Moreover, the destruction of C=Carom. bonds and interactions with aromatic rings are heightened. In contrast, the results of experiments in the absence of catalysts exposed polymerization and condensation of aromatic rings. The most remarkable result to emerge from the thermo-catalytic influence is the irreversible viscosity reduction of produced crude oil enhancing the oil recovery factor. Moreover, the introduction of catalysts increases the gas factor due to additional gas generation as a result of aquathermolysis reactions. The yield of methane gas is significantly high in the experimental runs with oil-saturated rocks rather than crude oil experiments. The gas factor reaches 45 m3/ton.

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Section: Resultsmentioning

confidence: 99%

Catalytic Aquathermolysis of Boca de Jaruco Heavy Oil with Nickel-Based Oil-Soluble Catalyst

et al. 2020

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“… 24 On the basis of these results and the results of experimental studies of the reaction products in the laboratory aquathermolysis process, 13 we suggest that the heterolytic cleavage via ionic routes is also the most preferable mechanism involved in the transition-metal-catalyzed aquathermolysis processes of heavy oils, which we have studied recently under laboratory conditions. 25 − 27 Even if the hydrolysis routes also involve ionic reaction schemes, they are characterized by rather high energy barriers according to the published results of ab initio calculations. 24 To compare these two possible mechanisms, i.e., heterolytic cleavage and hydrolysis, which are most likely involved in the processes of aquathermolysis of CPS under conditions of catalysis by transition-metal ions, we have calculated thermodynamic characteristics of these processes using rigorous quantum-chemical approaches.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Insights into the Catalytic Effect of Transition-Metal Ions on the Aquathermal Degradation of Sulfur-Containing Heavy Oil: A DFT Study of Cyclohexyl Phenyl Sulfide Cleavage

et al. 2020

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Steam injection is the most widely used technique for effectively reducing the viscosity of heavy oil in heavy oil production, in which in situ upgrading of heavy oil by aquathermolysis plays an important role. Earlier, transition-metal catalysts have been used for improving the efficiency of steam injection by catalytic aquathermolysis and achieving a higher degree of in situ oil upgrading. However, the unclear mechanism of aquathermolysis makes it difficult to choose efficient catalysts for different types of heavy oil. This theoretical study is aimed at deeply understanding the mechanism of in situ upgrading of sulfur-containing heavy oil and its catalysis. For this purpose, cyclohexyl phenyl sulfide (CPS) is selected as a model compound of sulfur-containing oil components, and, for the first time, a catalytic effect of transition metals on the thermochemistry and kinetics of its aquathermolysis is investigated by the density functional theory (DFT) methods with the use of the Becke three-parameter Lee–Yang–Parr (B3LYP), ωB97X-D, and M06-2X functionals. Calculation results show that the hydrolysis of CPS is characterized by fairly high energy barriers in comparison with other possible reaction routes leading to the cleavage of C–S bonds, while the heterolysis of C–S bonds in the presence of protons has a substantially lower kinetic barrier. According to the theoretical analysis, transition-metal ions significantly reduce the kinetic barrier of heterolysis. The Cu 2+ ion outperforms the other investigated metal ions and the hydrogen ion in the calculated rate constant by 5–6 (depending on the metal) and 7 orders of magnitude, respectively. The catalytic activity of the investigated transition-metal ions is arranged in the following sequence, depending on the used DFT functional: Cu 2+ ≫ Co 2+ ≈ Ni 2+ > Fe 2+ . It is theoretically confirmed that transition-metal ions, especially Cu 2+ , can serve as effective catalysts in aquathermolysis reactions. The proposed quantum-chemical approach for studying the catalytic aquathermolysis provides a new supplementary theoretical tool that can be used in the development of catalysts for different chemical transformations of heavy oil components in reservoirs due to hydrothermal treatment.

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“…Ni-W-S particles in ion liquid had a plate form with 0.5 nm thickness combined into agglomerates with diameters of 100-150 nm [88]. Several studies have been carried out on the efficiency of aquathermolysis catalysts based on metal (Fe, Co, Ni, Cu) tallates for extra-heavy oil samples of Boca de Jaruco with the viscosity of 270 Pa•s [89][90][91]. The content of asphaltenes in the given object was very high-20%.…”

Section: Oil-soluble Catalystsmentioning

confidence: 99%

In-Situ Heavy Oil Aquathermolysis in the Presence of Nanodispersed Catalysts Based on Transition Metals

et al. 2021

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The aquathermolysis process is widely considered to be one of the most promising approaches of in-situ upgrading of heavy oil. It is well known that introduction of metal ions speeds up the aquathermolysis reactions. There are several types of catalysts such as dispersed (heterogeneous), water-soluble and oil soluble catalysts, among which oil-soluble catalysts are attracting considerable interest in terms of efficiency and industrial scale implementation. However, the rock minerals of reservoir rocks behave like catalysts; their influence is small in contrast to the introduced metal ions. It is believed that catalytic aquathermolysis process initiates with the destruction of C-S bonds, which are very heat-sensitive and behave like a trigger for the following reactions such as ring opening, hydrogenation, reforming, water–gas shift and desulfurization reactions. Hence, the asphaltenes are hydrocracked and the viscosity of heavy oil is reduced significantly. Application of different hydrogen donors in combination with catalysts (catalytic complexes) provides a synergetic effect on viscosity reduction. The use of catalytic complexes in pilot and field tests showed the heavy oil viscosity reduction, increase in the content of light hydrocarbons and decrease in heavy fractions, as well as sulfur content. Hence, the catalytic aquathermolysis process as a distinct process can be applied as a successful method to enhance oil recovery. The objective of this study is to review all previously published lab scale and pilot experimental data, various reaction schemes and field observations on the in-situ catalytic aquathermolysis process.

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Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part III – changes in composition resins and asphaltenes

Cited by 37 publications

References 19 publications

Catalytic Aquathermolysis of Boca de Jaruco Heavy Oil with Nickel-Based Oil-Soluble Catalyst

Catalytic Aquathermolysis of Boca de Jaruco Heavy Oil with Nickel-Based Oil-Soluble Catalyst

Theoretical Insights into the Catalytic Effect of Transition-Metal Ions on the Aquathermal Degradation of Sulfur-Containing Heavy Oil: A DFT Study of Cyclohexyl Phenyl Sulfide Cleavage

In-Situ Heavy Oil Aquathermolysis in the Presence of Nanodispersed Catalysts Based on Transition Metals

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