Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining

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

Deadline for manuscript submissions: 31 March 2024 | Viewed by 19531

Special Issue Editors

Institute of Geology and Petroleum Technologies, Kazan Federal University, 18 Kremlyovskaya Str., Kazan 420008, Russia
Interests: EOR; heavy oil; aquathermolysis; catalysts; microscopy; nanotechnology
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, 4, Akademichesky Ave., 634055 Tomsk, Russia
Interests: heavy oil; in-situ catalysts; asphaltene transformations; thermal and catalytic cracking; mesoporous catalysts for petrochemical; transition metals

Special Issue Information

Dear Colleagues,

Nowadays, the tendency to decrease the explored reserves and the production of light and medium oil is clearly outlined; however, at the same time, the world demand for oil is continuously growing. The problem of the shortage of oil raw materials can be solved by exploring the processing of unconventional sources of hydrocarbons (heavy oils, natural bitumens, etc.) as well as increasing the depth of oil processing. By increasing the depth of refining and using heavy oils as feedstock, the yield of heavy oil residues that contain significant amounts of high-molecular-weight heteroatomic compounds will increase as well. These compounds cause difficulties in oil refining by contributing to the formation of coke and deactivating catalysts. To develop effective methods of refining heavy oils and natural bitumens and further usage of obtained products, it is necessary to obtain knowledge about the influence of temperature and the nature of catalysts on different functional groups in the structure of resins and asphaltenes molecules. These data are important for a deeper understanding of changes that occur in resins and asphaltenes during thermal and catalytic cracking processes, selection of optimal plant modernization schemes and determination of heavy hydrocarbon feedstock refining regimes by oil refiners.

Among various options for oil refining is the use of catalytic compositions directly in the porous medium of high-viscosity oil reservoir rocks in hydrothermal conditions, as well as the use of catalysts in oil refining. The most well-studied method is the injection of oil-soluble precursors on the basis of transition metals (iron, copper, cobalt, nickel, etc.) used to form an active catalyst form in situ. Such catalysts intensify mainly the processes of destruction of the least stable carbon-heteroatom bonds, and there is also a detachment of peripheral fragments from resins and asphaltenes with the formation of aliphatic and aromatic hydrocarbons, heteroatomic compounds and benzene resins that provides changes of elemental, group and fractional compositions of oil. The results obtained are important for creating a scientific basis for advanced technologies of rational use on heavy oils and natural bitumens, as well as optimizing the existing processes of the primary and advanced processing of heavy hydrocarbon raw materials.

Dr. Irek Mukhamatdinov
Dr. Nikita N. Sviridenko
Guest Editors

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Keywords

  • heavy oil
  • aquathermolysis
  • cracking
  • dispersed catalytic systems
  • hydroconversion
  • hydrogen donors
  • transition metals
  • in situ upgrading
  • petroleum refining

Published Papers (8 papers)

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Research

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20 pages, 3107 KiB  
Article
Enzymatic-Based Hydrolysis of Digested Potato Peel Wastes by Amylase Producing Fungi to Improve Biogas Generation
by Mohammed S. Almuhayawi, Elhagag A. Hassan, Khalil K. Alkuwaity, Turki S. Abujamel, Jawahir A. Mokhtar, Hatoon A. Niyazi, Saad B. Almasaudi, Turki A. Alamri, Azhar A. Najjar, Nidal M. Zabermawi, Essam I. Azhar, Rania M. Makki, Hanouf A. Niyazi and Steve M. Harakeh
Catalysts 2023, 13(5), 913; https://doi.org/10.3390/catal13050913 - 22 May 2023
Cited by 2 | Viewed by 1778
Abstract
Potato peel wastes are generated in high quantities from potato processing industries. They are pollutants to the environment, and they release greenhouse gases into the atmosphere. The present study assessed the potentiality of hydrolyzing potato wastes by amylase-producing fungi to improve biogas generation [...] Read more.
Potato peel wastes are generated in high quantities from potato processing industries. They are pollutants to the environment, and they release greenhouse gases into the atmosphere. The present study assessed the potentiality of hydrolyzing potato wastes by amylase-producing fungi to improve biogas generation from potato peels through the anaerobic digestion process. Different fungal isolates were screened for amylase production on potato wastes, and the highest amylase producer was selected for optimizing the efficacy of producing amylases in high quantities to efficiently allow the conversion of potato organic matter into fermentable sugars that are utilized for the anaerobic digestion process. The best amylase producers were those derived from Rhizopus stolonifer (32.61 ± 0.89 U/mL). The highest cumulative methane yield from hydrolyzed potato peel was 65.23 ± 3.9 mL CH4/g and the methane production rate was 0.39 mL CH4/h, whereas the highest biogas yield from unhydrolyzed potato wastes was 41.32 ± 2.15 mL CH4/g and the biogas production rate was 0.25 mL CH4/h. Furthermore, it was found that the two combined sequential stages of anaerobic digestion (biogas production) followed by biodiesel production (enzymatic esterification) were the most effective, recording 72.36 ± 1.85 mL CH4/g and 64.82% biodiesel of the total analytes. However, one-pot fermentation revealed that biogas yield was 22.83 ± 2.8 mL CH4/g and the biodiesel extracted was 23.67% of the total analytes. The insights of the current paper may increase the feasibility of potato peel-based biorefinery through the biological hydrolysis strategy of potato wastes using eco-friendly enzymes. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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12 pages, 2650 KiB  
Article
Integrated Modeling of the Catalytic Aquathermolysis Process to Evaluate the Efficiency in a Porous Medium by the Example of a Carbonate Extra-Viscous Oil Field
by Ilgiz F. Minkhanov, Vladislav V. Chalin, Aidar R. Tazeev, Alexander V. Bolotov, Irek I. Mukhamatdinov, Sergey A. Sitnov, Alexey V. Vakhin, Mikhail A. Varfolomeev, Sergey I. Kudryashov, Igor S. Afanasiev, Alexey V. Solovyev, Georgiy V. Sansiev, Dmitry A. Antonenko, Kirill A. Dubrovin and Iaroslav O. Simakov
Catalysts 2023, 13(2), 283; https://doi.org/10.3390/catal13020283 - 27 Jan 2023
Cited by 4 | Viewed by 1191
Abstract
In order to evaluate the efficiency of the catalytic aquathermolysis process, physical modeling was carried out on bituminous sediments of Paleocene–Miocene carbonate rocks, characterized by the presence of open and closed fractures. In this context, three filtration experiments were performed on an unextracted [...] Read more.
In order to evaluate the efficiency of the catalytic aquathermolysis process, physical modeling was carried out on bituminous sediments of Paleocene–Miocene carbonate rocks, characterized by the presence of open and closed fractures. In this context, three filtration experiments were performed on an unextracted reservoir model with extra-viscous oil (EVO). Prior to the experiments, the mineral composition of the rock was determined by X-ray diffraction analysis (XRD) and the content of organic matter and coking products was determined before and after the experiment by thermogravimetric analysis (TGA) as well as the group composition of oil (SARA) before and after the experiment by nuclear magnetic resonance (NMR), gas composition at the fluid separation line, and oil displacement coefficient (ODC). The results of the conducted experiments show that the efficiency of displacement of extraviscous oil could be significantly increased by the use of a solvent and the combined use of a solvent and a catalyst (+9.3% and +17.1% of the oil displacement coefficient, respectively), which is associated with the processes of oil refining. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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20 pages, 6957 KiB  
Article
Viscosity Reduction and Mechanism of Aquathermolysis of Heavy Oil Co-Catalyzed by Bentonite and Transition Metal Complexes
by Wangyuan Zhang, Qi Li, Yongfei Li, Sanbao Dong, Sen Peng and Gang Chen
Catalysts 2022, 12(11), 1383; https://doi.org/10.3390/catal12111383 - 07 Nov 2022
Cited by 5 | Viewed by 1845
Abstract
At present, the research on aquathermolysis catalysts mainly focuses on the catalytic effect of external catalysts on the reaction, ignoring the fact that external catalysts will form complexes with in situ inorganic minerals after entering the reservoir. In this paper, we investigated the [...] Read more.
At present, the research on aquathermolysis catalysts mainly focuses on the catalytic effect of external catalysts on the reaction, ignoring the fact that external catalysts will form complexes with in situ inorganic minerals after entering the reservoir. In this paper, we investigated the effects of transition metal complexes as external catalysts and bentonite as in situ catalysts on aquathermolysis, respectively. Meanwhile, the aquathermolysis reaction co-catalyzed by external and in situ catalysts was further investigated. The results show that the transition metal complexes exhibited good co-catalysis with bentonite. The viscosity reduction rate can reach 73.47% at 200 °C and 4 h with 0.1 wt.% of catalyst (NAD–Zn) addition. The addition of ethanol under the same reaction conditions will further increase the viscosity reduction rate to 84.59%. The results of thermogravimetric analysis, component analysis and boiling range analysis of heavy oil show that the heavy components in heavy oil are cracked into light components after the aquathermolysis. The results of elemental analysis show that the heteroatoms in the heavy oil were removed and the quality of the crude oil was improved. The results of GC–MS analysis of the model compounds showed that the process of aquathermolysis was mainly through the cleavage of C–C, C–N and C–S bonds to crack the macromolecules into small molecules, and then achieve the effect of viscosity reduction. The main mechanism of catalyst action is the acidic center on the surface of the bentonite and the coordination bonds formed by the transition metal complexes with the heteroatoms. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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22 pages, 4709 KiB  
Article
A Theoretical and Experimental Approach to the Analysis of Hydrogen Generation and Thermodynamic Behavior in an In Situ Heavy Oil Upgrading Process Using Oil-Based Nanofluids
by Oscar E. Medina, Santiago Céspedes, Richard D. Zabala, Carlos A. Franco, Agustín F. Pérez-Cadenas, Francisco Carrasco-Marín, Sergio H. Lopera, Farid B. Cortés and Camilo A. Franco
Catalysts 2022, 12(11), 1349; https://doi.org/10.3390/catal12111349 - 02 Nov 2022
Cited by 2 | Viewed by 1261
Abstract
This study aims to show a theoretical and experimental approach to the analysis of hydrogen generation and its thermodynamic behavior in an in situ upgrading process of heavy crude oil using nanotechnology. Two nanoparticles of different chemical natures (ceria and alumina) were evaluated [...] Read more.
This study aims to show a theoretical and experimental approach to the analysis of hydrogen generation and its thermodynamic behavior in an in situ upgrading process of heavy crude oil using nanotechnology. Two nanoparticles of different chemical natures (ceria and alumina) were evaluated in asphaltene adsorption/decomposition under a steam atmosphere. Then, a nanofluid containing 500 mg·L−1 of the best-performing nanoparticles on a light hydrocarbon was formulated and injected in a dispersed form in the steam stream during steam injection recovery tests of two Colombian heavy crude oils (HO1 and HO2). The nanoparticles increased the oil recovery by 27% and 39% for HO1 and HO2 regarding the steam injection. The oil recovery at the end of the displacement test was 85% and 91% for HO1 and HO2, respectively. The recovered crude oil showed an increment in API° gravity from 12.4° and 12.1° to 18.5° and 29.2° for HO1 and HO2, respectively. Other properties, such as viscosity and content of asphaltenes and resins with high molecular weight, were positively modified in both crude oils. The fugacity of H2 was determined between the reservoir and overburden pressure and different temperatures, which were determined by the thermal profiles in the displacement test. The fugacity was calculated using the application of virial equations of state with mixing rules based on the possible intermolecular interactions between the components. Hydrogen acquired a higher chemical potential via nanoparticle presence. However, the difference in H2 fugacity between both points is much higher with nanoparticles, which means that hydrogen presents a lower tendency to migrate by diffusion to the high-pressure point. The difference between HO1 and HO2 lies mainly in the fact that the pressure difference between the reservoir and the overburden pressure is greater in HO2; therefore, the difference in fugacity is greater when the pressure differential is greater. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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26 pages, 6370 KiB  
Article
Study of the Hydrothermal-Catalytic Influence on the Oil-Bearing Rocks of the Usinskoye Oil Field
by Irek I. Mukhamatdinov, Artem V. Lapin, Rezeda E. Mukhamatdinova, Aydar A. Akhmadiyarov, Boudkhil Affane, Dmitriy A. Emel’yanov, Olga V. Slavkina and Alexey V. Vakhin
Catalysts 2022, 12(10), 1268; https://doi.org/10.3390/catal12101268 - 18 Oct 2022
Cited by 2 | Viewed by 1272
Abstract
In this work, a synthesis of an oil-soluble iron-based catalyst precursor was carried out and its efficiency was tested in a laboratory simulation of the aquathermolysis process at different temperatures. The rocks of the Usinskoe field from the Permian deposits of the Komi [...] Read more.
In this work, a synthesis of an oil-soluble iron-based catalyst precursor was carried out and its efficiency was tested in a laboratory simulation of the aquathermolysis process at different temperatures. The rocks of the Usinskoe field from the Permian deposits of the Komi Republic, obtained by steam-gravity drainage, and the iron-based catalyst precursor, as well as the products of non-catalytic and catalytic aquathermolysis, were selected as the object of study. As a result, it was found that the content of alkanes in the samples after thermal steam treatment (TST) at 300 °C increased 8-fold compared to the original oil, and the content of cycloalkanes in the sample with the catalyst increased 2-fold compared to the control experience. This may indicate that not only the carbon-heteroatom bonds (C-S, N, O) but also the C-C bonds were broken. It also shows that increasing the iron tallate concentration at TST 300 °C leads to a decrease in the molecular mass of the oil compared to the control experiment. According to SEM, the catalyst is nanodisperse particles with a size of ≈60–80 nm, which are adsorbed on the rock surface, catalyst removal occurs at a small scale. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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14 pages, 1461 KiB  
Article
Effect of Hydrogen-Donor of Heavy Crude Oil Catalytic Aquathermolysis in the Presence of a Nickel-Based Catalyst
by Khoshim Kh. Urazov, Nikita N. Sviridenko, Yuliya A. Iovik, Ekaterina N. Kolobova, Maria V. Grabchenko, Irina A. Kurzina and Irek I. Mukhamatdinov
Catalysts 2022, 12(10), 1154; https://doi.org/10.3390/catal12101154 - 01 Oct 2022
Cited by 9 | Viewed by 1682
Abstract
The transformations of oil components from the Zyuzeevskoye field during catalytic aquathermolysis in the presence of a nickel-containing catalyst precursor and hydrogen donors were studied. It was found that the yield of gasoline and diesel fractions increased by more than 36% in the [...] Read more.
The transformations of oil components from the Zyuzeevskoye field during catalytic aquathermolysis in the presence of a nickel-containing catalyst precursor and hydrogen donors were studied. It was found that the yield of gasoline and diesel fractions increased by more than 36% in the case of catalytic aquathermolysis in the presence of tetralin. The maximum conversion of asphaltenes was achieved with a simultaneous slowing down of coke formation by four times. The calculation of the structural-group parameters of initial asphaltenes and the products of thermal cracking and catalytic aquathermolysis was made, and the hypothetical construction of their molecular structures was proposed. It was established that the phase composition, ratio, and morphology of nickel catalysts after catalytic aquathermolysis (CA) and catalytic aquathermolysis with tetralin (CA+T) depend on the amount of “free” hydrogen and are represented by Ni0.96S and Ni9S8. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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Review

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26 pages, 4136 KiB  
Review
FCC Catalyst Accessibility—A Review
by José Marcos Moreira Ferreira, Eduardo Falabella Sousa-Aguiar and Donato Alexandre Gomes Aranda
Catalysts 2023, 13(4), 784; https://doi.org/10.3390/catal13040784 - 21 Apr 2023
Cited by 2 | Viewed by 2769
Abstract
Fluid catalytic cracking (FCC) is a critical process in the petroleum-refining industry, designed to break down large hydrocarbon molecules into smaller, more valuable products. Fluid-cracking catalyst accessibility dramatically influences the efficiency of the FCC process. Accessibility is a catalyst feature related to the [...] Read more.
Fluid catalytic cracking (FCC) is a critical process in the petroleum-refining industry, designed to break down large hydrocarbon molecules into smaller, more valuable products. Fluid-cracking catalyst accessibility dramatically influences the efficiency of the FCC process. Accessibility is a catalyst feature related to the ease with which large feedstock molecules can penetrate the catalyst particle to reach the internal active sites where reactions occur—and the ease with which products desorb and leave the catalyst. Accessibility plays a vital role in the activity, selectivity, and life of the catalyst, and various techniques can be applied during the manufacturing process to accomplish its increase. This work reviews FCC catalyst accessibility, its characterization, and the ways to increase it, covering the past three decades of technical paper and patent literature. Bibliometric results of a literature search are presented, and a search strategy is described, encompassing database identification, keyword selection, refinement terms, search criteria, and result evaluation. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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23 pages, 2957 KiB  
Review
Enabling Catalysts for Biodiesel Production via Transesterification
by Baohua Wang, Bingquan Wang, Sudheesh K. Shukla and Rui Wang
Catalysts 2023, 13(4), 740; https://doi.org/10.3390/catal13040740 - 13 Apr 2023
Cited by 14 | Viewed by 6447
Abstract
With the rapid development of industry and the increasing demand for transportation, traditional sources of energy have been excessively consumed. Biodiesel as an alternative energy source has become a research focus. The most common method for biodiesel production is transesterification, in which lipid [...] Read more.
With the rapid development of industry and the increasing demand for transportation, traditional sources of energy have been excessively consumed. Biodiesel as an alternative energy source has become a research focus. The most common method for biodiesel production is transesterification, in which lipid and low carbon alcohol are commonly used as raw materials, in the presence of a catalyst. In the process of transesterification, the performance of the catalyst is the key factor of the biodiesel yield. This paper reviews the recent research progress on homogeneous and heterogeneous catalysts in biodiesel production. The advantages and disadvantages of current homogeneous acid catalysts and homogeneous base catalysts are discussed, and heteropolyacid heterogeneous catalysts and biomass-derived base catalysts are described. The applications of the homogeneous and heterogeneous catalyst derivatives ionic liquids/deep eutectic solvents and nanocatalysts/magnetic catalysts in biodiesel production are reviewed. The mechanism and economic cost of current homogeneous acid catalysts and homogeneous base catalysts are also analyzed. The unique advantages of each type of catalyst are compared to better understand the microscopic details behind biodiesel. Finally, some challenges of current biodiesel catalysts are summarized, and future research directions are presented. This review will provide general and in-depth knowledge on the achievements, directions, and research priorities in developing novel homogeneous/heterogeneous catalysts for the green and cost-effective production of biodiesel. Full article
(This article belongs to the Special Issue Catalysis for Bitumen/Heavy Oil Upgrading and Petroleum Refining)
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