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Vol 63, No 2 (2023)
Articles
Effect of Sub- and Supercritical Water on the Transformation of High-Molecular-Mass Components of High-Carbon Rocks from Unconventional Formations (A Review)
Abstract
State-of-the-art in the field of recovering high-molecular-mass hydrocarbon components of bituminous and shale rocks by intrastratum transformation into readily recoverable forms using sub- and supercritical water is analyzed. The phase composition of water and its properties in the critical state and the transformations of a number of substances in subcritical (SBW) and supercritical (SCW) water are discussed. The substances under consideration include model polycyclic and heteroatomic compounds containing nitrogen, sulfur, and oxygen, metal porphyrin complexes, asphaltenes, oil sands, and heavy oils and organic matter (OM) of kerogen-containing shale rocks. The preventing effect of hydrogen donors and catalysts for hydrogenation and oxidative cracking on the coking in the course of transformation of heavy hydrocarbons in SCW is compared. The catalytic effect of the mineral matrix of rocks in the course of generation of oil fractions from them is analyzed in detail. The published data concerning the possibility of using SBW and SCW for the transformation of high-molecular-mass components of high-carbon dense rocks from unconventional formations demonstrate high potential of hydrothermal and supercritical fluid technologies
145-179
8-Allyl-1,3-benzoxazines as Hydrogen Sulfide Corrosion Inhibitors and Biocides in Crude Oil Extraction
Abstract
The inhibitor and bactericidal properties of a series of allyl-substituted 1,3-benzoxazines and their water-soluble derivatives in hydrogen sulfide saturated water–salt–hydrocarbon systems were studied. The inhibitor properties of the compounds with respect to St.3 steel (St3Gsp, GOST (State Standard) 380-2005) strongly depend on the number of methylene groups in the substituents bonded to the nitrogen atom in the 1,3-oxazine ring. The bactericidal activity toward the growth of sulfate-reducing bacteria (SRB) also strongly depends on the structure of the compounds. With an increase in the number of methylene groups in the molecule, the protective properties of the compounds increase, whereas the bactericidal properties decrease. Compounds with an aromatic substituent at the nitrogen atom of the 1,3-oxazine ring exhibit higher inhibiting (maximal degree of protection ~97%) and bactericidal (maximal degree of SRB growth suppression ~100%) power.
180-190
SR Spectroscopy in Geochemical Studies of Asphaltenes of Crude Oils from Tatarstan Oil Fields
Abstract
ESR spectra of asphaltenes from a series of crude oils from the Devonian and Carboniferous deposits of the South-Tatar Dome in Tatarstan with low vanadium content and of vanadiferous crude oils from deposits of the Melekess depression in Tatarstan are analyzed. For asphaltenes from Devonian oils, the correlation between the concentrations of stable free radicals (SFR) and vanadyl complexes (VCs) has direct trend, whereas for asphaltenes from Carboniferous oils the trend is inverse. Taking into account the previously revealed inverse trend for asphaltenes of vanadium-enriched highly viscous crude oils [1], the opposite trends in SFR–VC correlations (direct and inverse) suggest different structures of asphaltene molecules in oils with different vanadium content and, correspondingly, different sources and conditions of the formation of oil deposits. Specific features of the ESR characteristics of asphaltenes of core and extractable oils and of oils from Devonian and Carboniferous deposits are revealed.
191-201
Oxidation of Sulfur Compounds by Sodium Hypochlorite over Molybdenum-Based Amphiphilic Catalysts
Abstract
The study reports on the oxidation of sulfur compounds by sodium hypochlorite over molybdenum-based amphiphilic catalysts. The conversion of dibenzothiophene (DBT) was investigated as a function of the catalyst composition and reaction conditions. When sodium hypochlorite was used in combination with the heptamolybdate-anion-containing amphiphilic catalyst, sulfur compounds were found to be effectively oxidized even at room temperature. Under optimum process conditions (an oxidant to sulfur molar ratio of 4 : 1, a catalyst concentration of 0.5 wt %, and an acetonitrile volume of 1 mL), 100% conversion of DBT to sulfone had already been achieved after ten min of oxidation. The addition of acetonitrile to the reaction mixture was found to minimize the aggregation of catalyst particles and enhance the process performance. The catalyst demonstrated sustained activity over five oxidation cycles without regeneration.
202-210
Oxidation of the Styrene Epoxide–Sulfuric Acid Binary System in an Alcohol Solution
Abstract
Oxygen uptake by the styrene epoxide (SE)–sulfuric acid (SA) binary system in a solution consisting of 90 vol % tert-butanol and 10 vol % chlorobenzene (BUC solvent) was studied. The equation for the reaction rate as a function of reactant concentrations and the Arrhenius equation for the effective oxidation rate constant are presented. Comparison of the results obtained with the data on oxidation in related binary systems SE–perchloric acid (PCA) and SE–p-toluenesulfonic acid (TSA) shows that the specific features of the oxidation of these systems are determined by the kind of the acid catalyst.
211-219
tert-Butyl Ethers of Renewable Diols as Oxygenated Additives for Motor Gasoline. Part I: Glycerol and Propylene Glycol Ethers
Abstract
The study investigates tert-butoxy alkanols (otherwise defined as polyol tert-butyl ethers) that have vicinal tert-butoxy and hydroxy groups in their molecules from the perspective of their usability as oxygenated additives for motor gasoline. A series of propylene glycol mono-tert-butyl ether (PTBE) and glycerol di-tert-butyl ether (di-GTBE) samples were prepared: PTBE by direct acid-catalytic alkylation of diols with tert-butanol, and di-GTBE by alkylation of epichlorohydrin. Adding PTBE and di-GTBE to base motor gasoline was found to improve its antiknock performance: the average blending research octane number to blending motor octane number ratios (bRON/bMON) equaled 120/111 and 124/104 for PTBE and di-GTBE, respectively. Furthermore, the effects of the ether additives on the properties of ethanol-blended base gasoline were characterized. Finally, the study describes the effect of polyol tert-butyl ether additives on the cloud point depression of ethanol-blended gasoline (low-temperature phase stabilization) and demonstrates a positive synergistic effect of adding the ethers mixed with ethanol
220-230
Filtration Performance of 3D-Printed Ceramic Pellets: Investigation Using CFD and Computed Tomography
Abstract
This study demonstrates the potential for computer-aided engineering and additive manufacturing techniques to fabricate protective layer materials with a novel design of filtration channels. Using computational fluid dynamics (CFD) simulation for channels of various geometries, potential locations of the capture of solid dust particles in ceramic filter pellets were identified. The filter pellets were fabricated from ceramic material using laser stereolithography. The printed samples were subjected to a filtration test. The CFD simulation of the pellet channels to identify potential filtration locations, followed by a comparative assessment of the simulation results and the post-test X-ray computed tomography (CT) scan of the 3D-printed pellets, demonstrated the feasibility of CFD models for the design of filter materials. The study findings are intended for the development of innovative protective materials with filtering capabilities to be implemented in specific industrial refining applications
231-238
Hydrogenation of CO2 over Biochar-Supported Catalysts
Abstract
The study investigates hydrogenation of CO2 over mono- and bimetallic catalysts supported on biochar. In this reaction, bimetallic iron–cobalt catalysts were shown to surpass monometallic iron and cobalt catalysts in terms of catalytic performance. The optimal combination of performance parameters was reached at an iron to cobalt ratio of 3 : 1. The composition and genesis of the active phase in the bimetallic Fe–Co catalyst were identified, and the CO2 hydrogenation mechanism was suggested for an iron-dominated bimetallic catalyst. Using biochar as a support was found to provide an active phase composition favorable for CO2 hydrogenation.
239-249
Dehydrogenation of Ethylbenzene to Styrene over Rhenium- and Tungsten-Containing Porous Ceramic Converters
Abstract
A series of tubular porous ceramic converters modified with mono- and bimetallic catalytic systems based on rhenium and tungsten were prepared by a combination of self-propagating high-temperature synthesis and the sol–gel method. These converters were tested in dehydrogenation of ethylbenzene to styrene. Among the tested samples, a monometallic tungsten-containing converter exhibited the optimal properties as it achieved the highest target product production performance. Within the temperature range of 550–600°C, this converter provided a yield of styrene up to about 15 wt % and styrene productivity up to about 22 g h–1 dm–3, with the carbonization of the sample not exceeding 5 wt % over about 6 h of reaction.
250-261
Partial Oxidation of Propane: Single-Site Pd/γ-Al2O3 Catalysts
Abstract
The paper proposes a method for synthesizing a heterogeneous catalyst that contains single Pd sites on γ-Al2O3 surface. This method involves preliminary heterogenization of a Pd complex with a hydroxyquinone (e.g., alizarin) on the γ-Al2O3 surface, followed by hydrogenolysis of the Pd–alizarin bond, reduction of Pd(II) into Pd(0), and removal of alizarin. The catalyst was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and tested in propane oxidation into key petrochemicals. During the test, the catalyst exhibited high activity (242 mol of the product per g-at Pd per hour).
262-267
Thermal Decomposition of Synthetic Cage Hydrocarbons and Their Mixtures
Abstract
The kinetics of thermal decomposition of cage hydrocarbons, specifically exo-tricyclo[5.2.1.02.6]decane (exo-TCD) and exo,endo-tetracyclo[5.3.1.02,6.08,10]undecane (TCU-1, a monocyclopropanated analog of exo-TCD), as well as their mixture (1 : 3 w/w) has been investigated. These compounds were compared in terms of thermal stability. The molar concentrations of the resultant gaseous products were determined experimentally. The equilibrium composition of the decomposition products was quantified, and the thermal effects of the thermal decomposition under thermodynamic and kinetic reaction control were identified.
268-276