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Catalysts
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Heavy Oil In Situ Upgrading and Catalysis
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Heavy Oil In Situ Upgrading and Catalysis

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 22103

Special Issue Editors

Dr. Alexey V. Vakhin

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Guest Editor
Institute of Geology and Petroleum Technologies, Kazan Federal University, 18 Kremlyovskaya St., P.O. Box 420008, Kazan, Russia
Interests: EOR; heavy oil; aquathermolysis; catalysts; thermal analysis; EM heating; nanotechnology
Special Issues, Collections and Topics in MDPI journals
Dr. Anton Lvovich Maksimov

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Guest Editor
1. Faculty of Chemistry, Moscow State University, Moscow, Russia
2. A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
Interests: synthesis of nano-sized unsupported catalysts for hydrocracking, hydrogenation, hydrodearomatization, and hydrotreatment; selective hydrogenation of unsaturated hydrocarbons and oxygen-containing compounds; producing fuels and additives by catalytic conversion of renewable feedstock; biphasic catalysis and catalysis in alternative media; immobilized catalysts; mesoporous and hybrid materials for petrochemical and organic synthesis

Special Issue Information

Dear Colleagues,

Nowadays, developing unconventional oil resources generates considerable interest in modern society due to the depletion of conventional oil resources. Heavy oil is widely believed to be the most important unconventional resource because of its tremendous reserves around the world. However, the exploitation of this type of energy source is still complicated in both recovery and transport stages due to their high viscosity and density, in addition to having a high content of resins and asphaltenes. Thus, to improve the production of heavy oil, experts have always considered thermally enhanced oil recovery to be a potential and promising approach for these purposes. Indeed, the thermal energy resulting from the application of thermally enhanced oil recovery contributes to heay oil viscosity reduction, in addition to reducing the amount of asphaltenes and resins as well. The next decade is likely to witness a rise in the application of thermally enhanced oil recovery methods for heavy and extra-heavy oil reservoirs. However, the characteristics of thermally enhanced oil recovery have not been addressed in detail. Thus, to improve these technologies, many researchers are considering the application of catalysts to be one of the main efficient approaches for decreasing heavy oil viscosity and hence facilitating its transportation. It is common knowledge that oil-soluble transition-metal-based catalysts play an important role in the heavy oil oxidation and pyrolysis reactions, in which they could decompose in situ and form active species in reservoir conditions in the form of nanoparticle suspensions or emulsions, leading to enhanced heavy oil recovery from these formations. These types of catalysts supposedly play the same role in downstream processes involving heavy oil processing by decreasing the amount of resins and asphaltenes content in the presence of hydrogen. Moreover, there is still be a wide gap in our knowledge about the mechanisms generated by injecting catalysts into the reservoir in a porous mineral medium and the role of the mineral surface as an active component of the catalytic complex. Thus, it is possible to use dispersed slurry systems and supported catalysts on specially selected carriers for better understanding. The present special issue is devoted to studying the problems related to catalysts synthesis, their formation, structure, and stability during heavy oil conversion during upgrading.

Dr. Alexey Vakhin
Dr. Anton Lvovich Maksimov
Guest Editors

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Keywords

  • heavy oil
  • aquathermolysis
  • cracking
  • catalyst
  • supported catalysts
  • specially selected carriers
  • dispersed catalytic systems
  • hydroconversion
  • hydrogen donors
  • transition metals
  • asphaltenes
  • in situ upgrading
 

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Published Papers (7 papers)

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Editorial

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3 pages, 177 KiB  
Editorial
Special Issue “Heavy Oil In Situ Upgrading and Catalysis”
by Alexey V. Vakhin, Mohammed Amine Khelkhal and Anton L. Maksimov
Catalysts 2023, 13(1), 99; https://doi.org/10.3390/catal13010099 - 3 Jan 2023
Cited by 6 | Viewed by 1673
Abstract
Until now, fossil fuels have played an important role in the daily life of human beings and civilization [...] Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)

Research

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16 pages, 3567 KiB  
Article
Transformation of Resinous Components of the Ashalcha Field Oil during Catalytic Aquathermolysis in the Presence of a Cobalt-Containing Catalyst Precursor
by Irek I. Mukhamatdinov, Indad Sh.S. Salih, Ilfat Z. Rakhmatullin, Nikita N. Sviridenko, Galina S. Pevneva, Rakesh K. Sharma and Alexey V. Vakhin
Catalysts 2021, 11(6), 745; https://doi.org/10.3390/catal11060745 - 18 Jun 2021
Cited by 16 | Viewed by 2752
Abstract
The aim of this work was to study the fractional composition of super-viscous oil resins from the Ashalcha field, as well as the catalytic aquathermolysis product in the presence of a cobalt-containing catalyst precursor and a hydrogen donor. The study was conducted at [...] Read more.
The aim of this work was to study the fractional composition of super-viscous oil resins from the Ashalcha field, as well as the catalytic aquathermolysis product in the presence of a cobalt-containing catalyst precursor and a hydrogen donor. The study was conducted at various durations of thermal steam exposure. In this regard, the work enabled the identification of the distribution of resin fractions. These fractions, obtained by liquid adsorption chromatography, were extracted with individual solvents and their binary mixtures in various ratios. The results of MALDI spectroscopy revealed a decrease in the molecular mass of all resin fractions after catalytic treatment, mainly with a hydrogen donor. However, the elemental analysis data indicated a decrease in the H/C ratio for resin fractions as a result of removing alkyl substituents in resins and asphaltenes. Moreover, the data of 1H NMR spectroscopy of resin fractions indicated an increase in the aliphatic hydrogen index during catalytic aquathermolysis at the high molecular parts of the resins R3 and R4. Finally, a structural group analysis was carried out in this study, and hypothetical structures of the initial oil resin molecules and aquathermolysis products were constructed as well. Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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22 pages, 4202 KiB  
Article
Extra-Heavy Oil Aquathermolysis Using Nickel-Based Catalyst: Some Aspects of In-Situ Transformation of Catalyst Precursor
by Alexey V. Vakhin, Firdavs A. Aliev, Irek I. Mukhamatdinov, Sergey A. Sitnov, Sergey I. Kudryashov, Igor S. Afanasiev, Oleg V. Petrashov and Danis K. Nurgaliev
Catalysts 2021, 11(2), 189; https://doi.org/10.3390/catal11020189 - 1 Feb 2021
Cited by 50 | Viewed by 3901
Abstract
In the present work, we studied the catalytic performance of an oil-soluble nickel-based catalyst during aquathermolysis of oil-saturated crushed cores from Boca de Jaruco extra-heavy oil field. The decomposition of nickel tallate and some aspects of in-situ transformation of the given catalyst precursor [...] Read more.
In the present work, we studied the catalytic performance of an oil-soluble nickel-based catalyst during aquathermolysis of oil-saturated crushed cores from Boca de Jaruco extra-heavy oil field. The decomposition of nickel tallate and some aspects of in-situ transformation of the given catalyst precursor under the steam injection conditions were investigated in a high-pressure batch reactor using XRD and SEM analysis methods. The changes in physical and chemical properties of core extracts after the catalytic aquathermolysis process with various duration were studied using gas chromatography for analyzing gas products, SARA analysis, GC-MS of saturated and aromatic fractions, FT-IR spectrometer, elemental analysis, and matrix-activated laser desorption/ionization (MALDI). The results showed that nickel tallate in the presence of oil-saturated crushed core under the injection of steam at 300 °C transforms mainly into nonstoichiometric forms of nickel sulfide. According to the SEM images, the size of nickel sulfide particles was in the range of 80–100 nm. The behavior of main catalytic aquathermolysis gas products such as CH4, CO2, H2S, and H2 depending on the duration of the process was analyzed. The catalytic upgrading at 300 °C provided decrease in the content of resins and asphaltenes, and increase in saturated hydrocarbon content. Moreover, the content of low-molecular alkanes, which were not detected before the catalytic aquathermolysis process, dramatically increased in saturates fraction after catalytic aquathermolysis reactions. In addition, the aromatics hydrocarbons saturated with high molecular weight polycyclic aromatic compounds—isomers of benzo(a)fluorine, which were initially concentrated in resins and asphaltenes. Nickel sulfide showed a good performance in desulfurization of high-molecular components of extra-heavy oil. The cracking of the weak C–S bonds, which mainly concentrated in resins and asphaltenes, ring-opening reactions, detachment of alkyl substitutes from asphaltenes and inhibition of polymerization reactions in the presence of catalytic complex reduced the average molecular mass of resins (from 871.7 to 523.3 a.m.u.) and asphaltenes (from 1572.7 to 1072.3 a.m.u.). Thus, nickel tallate is a promising catalyst to promote the in-situ upgrading of extra-heavy oil during steam injection techniques. Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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14 pages, 4628 KiB  
Article
A Comparison of Laboratory Simulation Methods of Iron Contamination for FCC Catalysts
by Yitao Liao, Tao Liu, Huihui Zhao and Xionghou Gao
Catalysts 2021, 11(1), 104; https://doi.org/10.3390/catal11010104 - 14 Jan 2021
Cited by 5 | Viewed by 2344
Abstract
Two different methods of simulating iron contamination in a laboratory were studied. The catalysts were characterized using X-ray diffraction, N2 adsorption–desorption, and SEM-EDS. The catalyst performance was evaluated using an advanced cracking evaluation device. It was found that iron was evenly distributed [...] Read more.
Two different methods of simulating iron contamination in a laboratory were studied. The catalysts were characterized using X-ray diffraction, N2 adsorption–desorption, and SEM-EDS. The catalyst performance was evaluated using an advanced cracking evaluation device. It was found that iron was evenly distributed in the catalyst prepared using the Mitchell impregnation method and no obvious iron nodules were found on the surface of the catalyst. Iron on the impregnated catalyst led to a strong dehydrogenation capacity and a slight decrease in the conversion and bottoms selectivity. The studies also showed that iron was mainly in the range of 1–5 μm from the edge of the catalyst prepared using the cycle deactivation method. Iron nodules could be easily observed on the surface of the catalyst. The retention of the surface structure in the alumina-rich areas and the collapse of the surface structure in the silica-rich areas resulted in a continuous nodule morphology, which was similar to the highly iron-contaminated equilibrium catalyst. Iron nodules on the cyclic-deactivated catalyst led to a significant decrease in conversion, an extremely high bottoms yield, and a small increase in the dehydrogenation capacity. The nodules and distribution of iron on the equilibrium catalyst could be better simulated by using the cyclic deactivation method. Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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12 pages, 4041 KiB  
Article
The Composition and Structure of Ultra-Dispersed Mixed Oxide (II, III) Particles and Their Influence on In-Situ Conversion of Heavy Oil
by Irek I. Mukhamatdinov, Aliya R. Khaidarova, Rumia D. Zaripova, Rezeda E. Mukhamatdinova, Sergey A. Sitnov and Alexey V. Vakhin
Catalysts 2020, 10(1), 114; https://doi.org/10.3390/catal10010114 - 13 Jan 2020
Cited by 34 | Viewed by 3818
Abstract
This paper discusses the role of magnetite in the conversion of heavy oil from the Ashal’cha reservoir. The effect of catalysts on the in-situ upgrading of heavy oil is directed on the reduction of high-molecular components of oil such as resins and asphaltenes [...] Read more.
This paper discusses the role of magnetite in the conversion of heavy oil from the Ashal’cha reservoir. The effect of catalysts on the in-situ upgrading of heavy oil is directed on the reduction of high-molecular components of oil such as resins and asphaltenes and their molecular masses. Moreover, it is directed on the significant increase in saturates and aromatic fractions. Measuring the temperature-dependent viscosity characteristics revealed the tremendous viscosity decrease of the obtained catalytic aquathermolysis products. X-ray analysis exposed the composition of the initial catalyst that consisted of mixed iron oxides (II, III), as well as catalysts that were extracted from the treated crude oil. The particle size of the catalysts was investigated by scanning electron microscopy. According to the SEM data, aggregates of 200 nm were formed that were in the range of ultra-dispersed particles (200 to 500 nm). Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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12 pages, 3696 KiB  
Article
Quantitative Visual Characterization of Contaminant Metals and Their Mobility in Fluid Catalytic Cracking Catalysts
by Corbett Senter, Melissa Clough Mastry, Alexander M. Mannion, Robert McGuire, Jr., Daniel Houtz and Bilge Yilmaz
Catalysts 2019, 9(10), 831; https://doi.org/10.3390/catal9100831 - 3 Oct 2019
Cited by 12 | Viewed by 2831
Abstract
A new approach for characterization of fluid catalytic cracking (FCC) catalysts is proposed. This approach is based on computational visual analyses of images originating from field emission scanning electron microscopy (FE-SEM) studies coupled with elemental mapping via electron dispersive x-ray spectroscopy (EDX) analyses. [...] Read more.
A new approach for characterization of fluid catalytic cracking (FCC) catalysts is proposed. This approach is based on computational visual analyses of images originating from field emission scanning electron microscopy (FE-SEM) studies coupled with elemental mapping via electron dispersive x-ray spectroscopy (EDX) analyses. The concept of contaminant metal mobility is defined and systematically studied through quantification of interparticle transfer and intraparticle penetration of the most common FCC contaminant metals (nickel, vanadium, iron, and calcium). This novel methodology was employed for practical quantification of intraparticle mobility via the Peripheral Deposition Index (PDI). For analyzing and quantifying interparticle mobility, a new index was developed and coined “Interparticle Mobility Index” or IMI. With the development and practical application of these two indices, this study offers the first standardized methodology for quantification of metals mobility in FCC. This novel systematic approach for analyzing metals mobility allows for improved troubleshooting of refinery-specific case studies and for more effective research and development in contaminant metals passivation in FCC catalysts. Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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19 pages, 7510 KiB  
Article
Ex-Situ Synthesis and Study of Nanosized Mo-Containing Catalyst for Petroleum Residue Hydro-Conversion
by Malkan Kh. Kadieva, Anton L. Maximov and Khusain M. Kadiev
Catalysts 2019, 9(8), 649; https://doi.org/10.3390/catal9080649 - 29 Jul 2019
Cited by 7 | Viewed by 3041
Abstract
This study represents the results of ex-situ synthesis and research of the properties of concentrated suspensions with new catalysts for petroleum residue hydro-conversion. Suspensions were prepared and stabilized in a petroleum residue medium through reverse emulsions containing water-soluble Mo-precursor and S-containing agents (elemental [...] Read more.
This study represents the results of ex-situ synthesis and research of the properties of concentrated suspensions with new catalysts for petroleum residue hydro-conversion. Suspensions were prepared and stabilized in a petroleum residue medium through reverse emulsions containing water-soluble Mo-precursor and S-containing agents (elemental sulfur, thiocarbamide) in the absence of a solid carrier. The resulting ex-situ catalyst dispersions had Mo content of 6–10 wt % and contained nanosized and submicron catalyst particles stabilized in a petroleum residue medium. The effects of S-containing agents on the properties of catalytic particles (sulfidation level, dispersity, structural and morphological features) were studied. The synthesis conditions for the optimal ex-situ catalyst providing the lowest coke yield (0.2 wt %) and the highest conversion (55.5 wt %) during petroleum residue hydro-conversion in a single pass mode have been determined. Full article
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)
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