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Catalysis in Aquathermolysis of Heavy Oil
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Catalysis in Aquathermolysis of Heavy Oil

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

Deadline for manuscript submissions: closed (20 December 2023) | Viewed by 11554

Special Issue Editors

Dr. Sergey A. Sitnov

E-Mail Website1 Website2
Guest Editor
Institute of Geology and Petroleum Technologies, Kazan (Volga Region) Federal University (KFU), 18 Kremlyovskaya St., P.O. Box, 420008 Kazan, Russia
Interests: research in the field of thermal and chemical enhanced oil recovery using catalysts for in situ heavy oil upgrading; design and synthesis of oil-soluble, nanosized catalysts and catalytic systems with hydrogen donors for the process of aquathermolysis; investigation of catalysts active form composition, structure, and their transformation after thermal influences; investigation of composition, structure, and transformation of heavy oil components after thermal influences; modernization of thermal heavy oil recovery technologies
Prof. Dr. Alexey Cheremisin

E-Mail Website1 Website2
Co-Guest Editor
Skolkovo Institute of Science and Technology, Bolshoy Boulevard 30, bld. 1, Moscow 121205, Russia
Interests: enhanced oil recovery; chemical EOR; gas EOR; thermal EOR; digital rock; reservoir physics; multiphase flow; hydraulic fracturing; special core analysis; microfluidics; hydrogen production
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Nowadays, the current global trend is focusing on actively developing heavy oil deposits, which requires the use of unconventional production methods. In fact, thermal enhanced oil recovery methods are occupying a prevailing place among other unconventional enhanced oil recovery methods, in particular, injection of superheated steam (cyclic steam injection, steam-assisted gravity drainage, etc.). Such an impact on the reservoir, due to high temperature and the presence of catalytically active rocks minerals, may lead to improvements in the composition of the produced oil and its decreased viscosity. This process is called aquathermolysis, as recommended by Hyne and co-workers. However, at the same time, the high temperature promotes the removal of gaseous products and the formation of free radicals which initiate condensation reactions, and the viscosity of the oil at the surface becomes even higher. All this leads to an increase in capital and operating costs as obstacles for the development of the field as a whole.

The development of special reagents that would maintain the high mobility of heavy oil during production and thereby increase the energy efficiency of thermal technologies is important and relevant. Such reagents can be present in various catalytic systems. Actually, various compounds of transition metals formed in situ from oil-soluble precursors as well as directly stabilized suspensions or emulsions of nanoparticles can be used as such catalysts for oil aquathermolysis reactions.

It is also important to study the influence of various factors on the efficiency of catalytic systems during the conversion of certain compounds and their groups that make up heavy oil, such as resin and asphaltene components. In addition to this, the metal nature of the catalyst, the morphology and sizes of its particles, as well as the spatial arrangement of metals in the crystal lattice in the case of bi- and polymetallic catalysts are also important factors to study during aquathermolysis processes.

Establishing the relationship between the composition, size, and morphology of catalyst particles and their cracking activity during in situ upgrading of heavy and extra-heavy oil in superheated steam environments will facilitate the development of modern enhanced heavy oil production technologies.

Dr. Sergey A. Sitnov
Prof. Dr. Alexey Cheremisin
Guest Editor

Manuscript Submission Information

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Keywords

  • aquathermolysis
  • heavy oil
  • cracking
  • catalyst
  • transition metals
  • dispersed catalysts
  • supported catalysts
  • oil-soluble catalysts
  • conversion
  • hydrogen donors
  • asphaltenes
  • coke
  • in situ upgrading

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Published Papers (5 papers)

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Research

25 pages, 9947 KiB  
Article
Experimental Study of Catalytically Enhanced Cyclic Steam-Air Stimulation for In Situ Hydrogen Generation and Heavy Oil Upgrading
by Pavel Afanasev, Alexey Smirnov, Anastasia Ulyanova, Evgeny Popov and Alexey Cheremisin
Catalysts 2023, 13(8), 1172; https://doi.org/10.3390/catal13081172 - 30 Jul 2023
Cited by 12 | Viewed by 1622
Abstract
The current study was performed for the experimental modeling of cyclic steam-air injection in a heavy oil reservoir model of dual porosity in the presence of a nickel-based catalyst for in situ oil upgrading enhanced by simultaneous hydrogen generation. The research was realized [...] Read more.
The current study was performed for the experimental modeling of cyclic steam-air injection in a heavy oil reservoir model of dual porosity in the presence of a nickel-based catalyst for in situ oil upgrading enhanced by simultaneous hydrogen generation. The research was realized in the combustion tube setup with a sandpack core model under reservoir conditions due to the consistent injection of air followed by oil in situ combustion (ISC) and steam (water) injection. As a result, the original oil was upgraded regarding fractional composition and oil properties. In addition, simulated reservoir heterogeneity and cyclic stimulation intensified the hydrogen synthesis, which, in turn, could also contribute to oil upgrading. Full article
(This article belongs to the Special Issue Catalysis in Aquathermolysis of Heavy Oil)
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13 pages, 1852 KiB  
Article
Influence of FeP and Al(H2PO4)3 Nanocatalysts on the Thermolysis of Heavy Oil in N2 Medium
by Yasser I. I. Abdelsalam, Renat F. Khamidullin, Vladimir E. Katnov, Aleksey V. Dengaev, Firdavs A. Aliev and Alexey V. Vakhin
Catalysts 2023, 13(2), 390; https://doi.org/10.3390/catal13020390 - 10 Feb 2023
Cited by 4 | Viewed by 1670
Abstract
The high viscosity of heavy oil is the main challenge hindering its production. Catalytic thermolysis can be an effective solution for the upgrading of heavy oil in reservoir conditions that leads to the viscosity reduction of native oil and increases the yield of [...] Read more.
The high viscosity of heavy oil is the main challenge hindering its production. Catalytic thermolysis can be an effective solution for the upgrading of heavy oil in reservoir conditions that leads to the viscosity reduction of native oil and increases the yield of light fractions. In this study, the thermolysis of heavy oil produced from Ashalchinskoye field was carried out in the presence of FeP and Al(H2PO4) nanocatalysts at a temperature of 250 °C in N2 gas environment. It was shown that Al(H2PO4)3 and FeP catalysts at a concentration of 0.5% significantly promoted the efficiency of the heavy oil thermolysis and are key controlling factors contributing to the acceleration of chemical reactions. The Al(H2PO4)3 + NiCO3 nanoparticles were active in accelerating the main chemical reactions during upgrading of heavy oil: desulfurization, removal of the side alkyl chains from polyaromatic hydrocarbons, the isomerization of the molecular chain, hydrogenation and ring opening, which led to the viscosity reduction in heavy oil by 42%wt. Moreover, the selectivity of the Al(H2PO4)3 + NiCO3 catalyst relative to the light distillates increased up to 33.56%wt., which is more than two times in contrast to the light distillates of initial crude oil. The content of resins and asphaltenes in the presence of the given catalytic complex was reduced from 34.4%wt. to 14.7%wt. However, FeP + NiCO3 nanoparticles contributed to the stabilization of gasoline fractions obtained after upgraded oil distillation. Based on the results, it is possible to conclude that the thermolysis of heavy oil in the presence of FeP and Al(H2PO4)3 is a promising method for upgrading heavy oil and reducing its viscosity. Full article
(This article belongs to the Special Issue Catalysis in Aquathermolysis of Heavy Oil)
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12 pages, 2094 KiB  
Article
Catalytic Low-Temperature Thermolysis of Heavy Oil in the Presence of Fullerene C60 Nanoparticles in Aquatic and N2 Medium
by Yasser I. I. Abdelsalam, Firdavs A. Aliev, Renat F. Khamidullin, Aleksey V. Dengaev, Vladimir E. Katnov and Alexey V. Vakhin
Catalysts 2023, 13(2), 347; https://doi.org/10.3390/catal13020347 - 3 Feb 2023
Cited by 3 | Viewed by 1825
Abstract
Catalytic thermolysis is considered to be an effective process for viscosity reduction, the conversion of high-molecular components of oil (resins and asphaltenes) into light hydrocarbons, and the desulfurization of hydrocarbons. In this paper, we conducted non-catalytic and catalytic thermolysis of a heavy oil [...] Read more.
Catalytic thermolysis is considered to be an effective process for viscosity reduction, the conversion of high-molecular components of oil (resins and asphaltenes) into light hydrocarbons, and the desulfurization of hydrocarbons. In this paper, we conducted non-catalytic and catalytic thermolysis of a heavy oil sample isolated from the Ashalcha oil field (Tatarstan, Russia) at a temperature of 250 °C. Fullerene C60 nanoparticles were applied to promote selective low-temperature thermolytic reactions in the heavy oil, which increase the depth of heavy oil upgrading and enhance the flow behavior of viscous crude oil. In addition, the influence of water content on the performance of heavy oil thermolysis was evaluated. It was found that water contributes to the cracking of high-molecular components such as resins and asphaltenes. The destruction products lead to the improvement of group and fractional components of crude oil. The results of the experiments showed that the content of asphaltenes after the aquatic thermolysis of the heavy oil sample in the presence of fullerene C60 was reduced by 35% in contrast to the initial crude oil sample. The destructive hydrogenation processes resulted in the irreversible viscosity reduction of the heavy oil sample from 3110 mPa.s to 2081 mPa.s measured at a temperature of 20 °C. Thus, the feasibility of using fullerene C60 as an additive in order to increase the yield of light fractions and reduce viscosity is confirmed. Full article
(This article belongs to the Special Issue Catalysis in Aquathermolysis of Heavy Oil)
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16 pages, 2347 KiB  
Article
Underground Upgrading of the Heavy Crude Oil in Content-Saturated Sandstone with Aquathermolysis in the Presence of an Iron Based Catalyst
by Sergey A. Sitnov, Irek I. Mukhamatdinov, Dmitry A. Feoktistov, Yaroslav V. Onishchenko, Vladislav A. Sudakov, Marat I. Amerkhanov and Alexey V. Vakhin
Catalysts 2021, 11(10), 1255; https://doi.org/10.3390/catal11101255 - 19 Oct 2021
Cited by 12 | Viewed by 2480
Abstract
Increasing the efficiency of thermal recovery methods is an important and relevant task. This study is devoted to reducing heavy components (resins and asphaltenes) and quality improvement of heavy oil by catalytic hydrothermal treatment. The object of this study is a bituminous sandstone [...] Read more.
Increasing the efficiency of thermal recovery methods is an important and relevant task. This study is devoted to reducing heavy components (resins and asphaltenes) and quality improvement of heavy oil by catalytic hydrothermal treatment. The object of this study is a bituminous sandstone sample from the Ashal’cha reservoir. The catalytic (iron tallate) hydrothermal simulation was carried out under reservoir conditions (200 °C, 30 bar). The composition and physicochemical characteristics of the products were studied using elemental and SARA analysis, MALDI, GC-MS, FT-IR. Moreover, the extracted rock is analyzed in XRD and DSA (Drop Shape Analyzer). The introduction of catalyst in combination with a hydrogen donor reduces the content of resins by 22.0%wt. with an increase in the share of saturated hydrocarbons by 27%wt. The destructive hydrogenation leads to a decrease in the sulfur content of upgrading products. This is crucial for the oil reservoirs of the Tatarstan Republic, as their crude oils are characterized by high sulfur content. According to the wettability data, the hydrophilicity of the rock surface increases due to inhibition of the coke formation after the introduction of the catalytic complex. Thus, the oil recovery factor can be increased due to the alteration of the oil-wetting properties of reservoir rocks. Full article
(This article belongs to the Special Issue Catalysis in Aquathermolysis of Heavy Oil)
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16 pages, 3714 KiB  
Article
Conversion of Residual Palm Oil into Green Diesel and Biokerosene Fuels under Sub- and Supercritical Conditions Employing Raney Nickel as Catalyst
by Eduardo Falabella Sousa-Aguiar, Carolina Zanon Costa, Maria Antonieta Peixoto Gimenes Couto, Débora de Almeida Azevedo and José Faustino Souza de Carvalho Filho
Catalysts 2021, 11(8), 995; https://doi.org/10.3390/catal11080995 - 19 Aug 2021
Cited by 3 | Viewed by 2633
Abstract
A comprehensive study of the thermal deoxygenation of palm residue under sub- and supercritical water conditions using Raney nickel as a heterogeneous catalyst is presented in this paper. Hydrothermal technology was chosen to replace the need for hydrogen as a reactant, as happens, [...] Read more.
A comprehensive study of the thermal deoxygenation of palm residue under sub- and supercritical water conditions using Raney nickel as a heterogeneous catalyst is presented in this paper. Hydrothermal technology was chosen to replace the need for hydrogen as a reactant, as happens, for example, in catalytic hydrotreatment. Several experiments were carried out at different reaction temperatures (350, 370, and 390 °C) and were analyzed with different times of reaction (1, 3.5, and 6 h) and catalyst loads (5, 7.5, 10 wt.%). No hydrogen was introduced in the reactions, but it was produced in situ. The results showed the selectivity of biokerosene ranged from 2% to 67%, and the selectivity of diesel ranged from 5% to 98%. The best result was achieved for 390 °C, 10 wt.% catalyst load, and 3.5 h of reaction, when the selectivities equal to 67% for biokerosene and 98% for diesel were obtained. The Raney nickel catalyst demonstrated a tendency to promote the decarboxylation reaction and/or decarbonylation reaction over the hydrodeoxygenation reaction. Moreover, the fatty acid and glycerol reforming reaction and the water−gas shift reaction were the main reactions for the in situ H2 generation. This study demonstrated that a hydrothermal catalytic process is a promising approach for producing liquid paraffin (C11−C17) from palm residue under the conditions of no H2 supply. Full article
(This article belongs to the Special Issue Catalysis in Aquathermolysis of Heavy Oil)
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