Petroleum Chemistry (v.53, #3)

Modeling of oil generation by Domanik carbonaceous shale by D. A. Bushnev; N. S. Burdel’naya (145-151).
Experiments on artificial maturation of carbonaceous rock of the Domanik age in an autoclave in the presence of water at temperatures of 250, 275, 300 and 325°C have been performed. It has been shown that a significant amount of soluble organic matter (OM) is produced from insoluble OM under these conditions. Changes have been observed in both the biomarker composition of the bitumen and the Rock-Eval OM maturity parameters characteristic of natural catagenesis. By the solid-state 13C NMR technique, it has been shown that the amount of aliphatic units decreases and that of aromatic units increases in residual kerogen. Study the product composition of the pyrolysis of residual kerogen has revealed that the relative amount of precursors of n-alkyl structures increases as compared with low-molecular-weight aromatic and thiophenic structures.
Keywords: Domanik shale; simulation of catagenesis; biomarkers; kerogen structure

Fischer-Tropsch synthesis in a slurry reactor in the presence of nanosized cobalt catalysts synthesized in situ in a hydrocarbon medium by S. N. Khadzhiev; A. Yu. Krylova; M. V. Kulikova; A. S. Lyadov; S. A. Sagitov (152-156).
Fischer-Tropsch synthesis in a slurry reactor at a pressure of 20 atm and a temperature of 220–300°C in the presence of 100Co : 2Pd : (5–50)Al2O3 and 100Co : 2Pd : (20–50)ZrO2 (parts by weight) catalysts in situ synthesized in a hydrocarbon medium has been studied. The catalysts were prepared by the decomposition of cobalt salts and promoters in melted petroleum paraffin P-2 at 300°C and in situ reduced with hydrogen. It has been found that the nanocatalyst containing 20 parts by weight of ZrO2 exhibits the highest activity in the Fischer-Tropsch synthesis and provides the yield of liquid products of 70 g/m3 at a CO conversion of 80%.
Keywords: synthetic liquid fuel; syngas; Fischer-Tropsch catalysts; nanocatalysts; slurry reactor

Hydrogenation of phenols in ionic liquids on rhodium nanoparticles by A. L. Maksimov; S. N. Kuklin; Yu. S. Kardasheva; E. A. Karakhanov (157-163).
A new catalyst system based on rhodium nanoparticles stabilized by polyacrylic acid have been suggested for the hydrogenation of phenols in ionic liquids. It has been shown that high near-quantitative yields of reaction products are achieved in ionic liquids containing a tetraalkylammonium cation. By the TEM and XPS techniques it has been revealed that the use of ionic liquids substantially decreases the particle size and reduces the aggregation of nanoparticles through the inclusion of the ionic liquid cations into the surface layer along with polyacrylic acid.
Keywords: hydrogenation; phenols; rhodium nanoparticles; ionic liquids

Recovery of the diesel fraction of oil sludge by engaging in the deep hydrotreating process for manufacturing ultraclean diesel fuels by V. Yu. Pivsaev; M. S. Kuznetsova; M. V. Samsonov; V. V. Ermakov; P. A. Nikulshin; A. A. Pimenov; A. A. Pimerzin; D. E. Bykov (164-170).
The possibility of involvement of diesel fractions obtained from petroleum waste in hydrotreating feedstock for the manufacture of diesel fuels that meet the Euro-4 and Euro-5 standards has been studied. The hydrogen treatment of a mixed feedstock, composed of diesel fractions of oil sludge (DFS), straight-run diesel fraction (SDF), and light catalytically cracked gas (LCCGO), conducted in a laboratory flow unit using the HTRU-120 CoMo/Al2O3 catalyst (340–360°C, 3.5 and 4.0 MPa, LHSV of 1.5–2.0 h−1, the hydrogen : feedstock ratios of 350 and 500 nL/L) has revealed that DFS can be used as a feedstock component for hydrotreating units used to manufacture diesel fuel that meets the Euro 4 and Euro 5 standards. If the process parameters of severe hydrogen treatment are maintained, as large an amount of DFS as 5 wt % can be involved in the hydrotreating unit feedstock. The samples of stabilized hydrogenation products obtained from this feedstock meet all the requirements of GOST (State Standard) R 52368-2005.
Keywords: hydrotreating; oil sludge; recovery; diesel fuel

The role of N-hydroxyphthalimide in the reaction mechanism of liquid-phase oxidation of p-cymene by V. N. Sapunov; G. N. Koshel’; Yu. B. Rumyantseva; E. A. Kurganova; N. D. Kukushkina (171-176).
The reaction of the liquid-phase oxidation of p-cymene to hydroperoxide with a selectivity of up to 95% at a hydrocarbon conversion of 25–30% has been studied at a reaction temperature of 80–120°C in the presence of N-hydroxyphthalimide as the catalyst. The catalytic role of N-hydroxyphthalimide has been substantiated. A kinetic model of the liquid-phase oxidation reaction in the presence of the catalyst N-hydroxyphthalimide has been developed and adequately described.
Keywords: liquid-phase oxidation; p-cymene; N-hydroxyphthalimide; p-cresol manufacture

Hydrotreating of mixtures of diesel fractions with gasoline and light coker gas oil by P. S. Solmanov; N. M. Maximov; Yu. V. Eremina; E. O. Zhilkina; Yu. Yu. Dryaglin; N. N. Tomina (177-180).
Involvement of gasoline and light coker gas oil in the feedstock of diesel hydrotreating units has been examined under laboratory conditions. The influence of the feedstock composition and the process conditions on the chemical composition and quality characteristics of the products has been revealed.
Keywords: coking distillates; straight-run diesel fraction; hydrotreating of products of secondary processes

Natural iron-containing materials and catalysts on their basis on use for photocatalytic decomposition of hydrogen sulfide by N. A. Zakarina; L. D. Volkova; O. K. Kim; A. R. Brodskii; I. F. Latypov; V. I. Yaskevich; L. V. Komashko (181-186).
A comparative study has been performed on the activity of natural iron-containing catalysts, such as Tagan montmorillonite in the iron form (FeMM), shale, iron-pillared (2,5 mmol Fe/g of MM) montmorillonite in the sodium form (NaMM), and NaMM-supported iron catalysts, in the photocatalytic decomposition reaction of concentrated (to 90%) hydrogen sulfide under UV and solar irradiation. It has been shown that the catalyst based on the natural MM in the iron form exhibits the highest activity. On the basis of electron microscopy and Mössbauer spectroscopy data, it has been assumed that the process is mediated by ultrafine particles of reduced iron forms.
Keywords: iron-containing catalysts; shale; hydrogen sulfide; catalyst activity

Catalytic transformations of mixtures of ethers with aliphatic and aromatic nitriles on solid acids under supercritical conditions by N. Ya. Usachev; V. P. Kalinin; E. A. Udal’tsova; A. V. Kazakov; E. P. Belanova; N. D. Kagramanov (187-193).
The catalytic conversion of mixtures of ethers with aliphatic and aromatic nitriles in supercritical conditions on zeolites (HY, HCaREEY), individual oxides (Al2O3, SiO2, MoO3, WO3, TiO2), and oxide systems (Al2O3-SiO2, H8[Si(Mo2O7)5], Al2(WO4)3) has been studied. It has been found that acid catalysts, such as zeolites, mixed oxides, and TiO2 (anatase), are active at 350°C in the direct synthesis of N-acylpyrrolidines from tetrahydrofuran and nitriles (CH3CN, n-C4H9CN, C6H5CN): the product yield reaches 40% and the selectivity is 65–94%. The activity and selectivity of TiO2 samples increase with an increase in the specific surface area (from 37 to 139 m2/g) or with a decrease in the particle size of anatase (from 43 to 13 nm according to XRD data). The character of interaction of the components of the reaction mixture with the TiO2 surface has been studied by the TG-DTA technique. After oxidative regeneration, TiO2 exhibits the initial catalytic properties, suggesting the possibility of its repeated use in the direct synthesis of acylpyrrolidines. Replacing THF by other compounds (diethyl ether, 1,4-dioxane, tetrahydropyran) drastically reduces the yield of respective alkylamides.
Keywords: oxides; solid acids; supercritical fluid conditions; ether; nitriles; acylpyrrolidines

Effect of solvent nature on the catalytic hydroformylation of 2,3-dihydrofuran by E. Yu. Wol’f; M. M. Vartanyan; A. L. Lapidus (194-196).
The effect of the solvent nature on the process of hydroformylation of 2,3-dihydrofuran in the presence of the phosphine-containing, complex Rh catalyst HRh(CO)(PPh3)3 has been studied. The influence of solvent polarity and basicity on the conversion of 2,3-dihydrofuran has been revealed, and the composition of tetrahydrofuran aldehydes and the selectivity of their formation have been determined.
Keywords: hydroformylation; 2,3-dihydrofuran; phosphine-containing complex; rhodium catalysts; 2-formyltetrahydrofuran; 3-formyltetrahydrofuran

Catalytic properties of polymer matrix-immobilized cobalt complexes with sulfonated phthalocyanines by A. S. Vashurin; R. A. Badaukaite; N. A. Futerman; S. G. Pukhovskaya; G. P. Shaposhnikov; O. A. Golubchikov (197-200).
Enhancement of the catalytic activity of phthalocyanine catalysts by their immobilizing on polymer matrices has been studied. It has been found that the immobilization of sulfonated cobalt phthalocyanines on polymers enhances their catalytic activity in the oxidation of sodium diethyldithiocarbamate with air oxygen under mild conditions.
Keywords: catalysis; phthalocyanines; complexes; polymer matrix

Oxidative desulfurization of catalytically cracked gasoline with hydrogen peroxide by E. V. Rakhmanov; A. V. Anisimov; A. V. Tarakanova; N. S. Baleeva; D. Guluzade (201-204).
Hydrogen peroxide desulfurization at 50°C of a catalytically cracked gasoline fraction containing methyl- and dimethylthiophenes and traces of benzothiophene and dibenzothiophene and boiling in the range of IBP-70°C in the presence of transition metal compounds Na2MoO4, Na2WO4, VOSO4, and [Cu(NH3)4]CO3 followed by adsorption on alumina has been studied. The successive oxidation of the hydrocarbon fraction in the presence of the copper and molybdenum compounds under phase transfer conditions ensures the removal of up to 96% of total sulfur.
Keywords: desulfurization; hydrogen peroxide; gasoline; catalytic cracking; peroxo complexes; transition metals

Detection of a heterophase upon liquid-phase oxidation of lubricating oils by A. A. Mukhin; S. Yu. Polyakov; S. I. Teterev; V. K. Fadeev; V. N. Bakunin (205-208).
By optical microscopy, it has been shown that the liquid-phase oxidation of mineral oils exemplified by the TP-22s oil leads to the formation of a heterophase system at the early stages. The size and images of the associates formed are presented, and the mechanism of their formation is proposed.
Keywords: mineral oil; liquid-phase oxidation; heterophase system; bulky associates; lacquer formation