Composition of Oil after Hydrothermal Treatment of Cabonate-Siliceous and Carbonate Domanic Shale Rocks

The hydrocarbon compositions of shale oils, generated from two different lithological–facial Domanic deposits of the Tatarstan Republic (Russia), were studied under hydrothermal impact with 30% of water addition in a 350 °С and CO2 environment. The samples were extracted from carbonate–siliceous rocks of the Semiluky–Mendym deposits of the Berezovskaya area, and carbonate deposits of the Dankovo–Lebedyan horizon of the Zelenogorskaya area of the Romashkino oil field. The distinctive features of rocks are in the composition and content of organic matter (OM), its thermal stability, as well as the structural-group composition of the shale oil products. The hydrothermal treatment of the rock samples increased the content of saturates and decreased the content of aromatics, resins and asphaltenes in the composition of crude oil. The decomposition of the polymer-like kerogen structure and destruction processes of high-molecular compounds, such as resins and asphaltenes, are accompanied with the formation of substances highly rich in carbons—carbenes and carboids. The contents of n-alkanes and acyclic isoprenoids increase in the composition of saturated hydrocarbons. According to the chemical classification of Al. A. Petrov, the character of the molecular mass distribution of such substances corresponds to oil type A1, which is considered paraffinic. The contents of dibenzothiophene, naphthalene and phenanthrene are increased in the composition of aromatic hydrocarbons, while the contents of tri-methyl-alkyl-benzene and benzothiophene are decreased. The increase in the aryl isoprenoid ratio (AIR = С13–С17/С18–С22) and maturity parameter (4-MDBT/1-MDBT) under the influences of hydrothermal factors indicates the increasing thermal maturity degree of the hydrocarbon system. The differences in the distribution behavior of saturated and aromatic hydrocarbons—biomarkers in rocks of various lithological-facies types, which are reasoned by different conditions of initial organic matter transformation as well as under the impact of hydrothermal factors—were revealed.

Change in the Structure of Asphaltene Macromolecules of the Krapivinskoye Oil Field During Biological Oxidation

Using physico-chemical methods of research (elemental analysis, infrared spectroscopy, selective chemical destruction of sulfide and ester bonds, chromatomass spectrometry) the influence of biodegradation processes on the composition and structure of asphaltenes of light oil at the Krapivinskoye deposit was studied. The results of comparative characteristics of initial asphaltenes and asphaltenes after biodestruction are presented. Attention is paid to studying their structural parameters and composition of fragments bound in asphaltene molecules through ester and sulfide bridges. It has been shown that microbial oxidation of asphaltenes of light oil by aboriginal soil microflora (laboratory experiment) occurs through a series of catalytic processes with formation of intermediate products of transformation – alcohols, aldehydes, ketones and fatty acids. It has been established that “grey and ether-bound” fragments in asphaltene molecules of biodegradable oil differ from “bound” compounds in the structure of the original asphaltenes with the qualitative composition of saturated and aromatic hydrocarbons and heteroatomic components

Heavy Oil Hydrocarbons and Kerogen Destruction of Carbonate–Siliceous Domanic Shale Rock in Sub- and Supercritical Water

This paper discusses the results of the influences of subcritical (T = 320 °C; P = 17 MPa) and supercritical water (T = 374 °C; P = 24.6 MPa) on the yield and composition of oil hydrocarbons generated from carbonaceous–siliceous Domanic shale rocks with total organic content (Corg) of 7.07%. It was revealed that the treatment of the given shale rock in sub- and supercritical water environments resulted in the decrease of oil content due to the intensive gas formation. The content of light hydrocarbon fractions (saturated and aromatic hydrocarbons) increased at 320 °C from 33.98 to 39.63%, while at 374 °C to 48.24%. Moreover, the content of resins decreased by almost twice. Insoluble coke-like compounds such as carbene–carboids were formed due to decomposition of kerogen after supercritical water treatment. Analysis of oil hydrocarbons with FTIR method revealed a significant number of oxygen-containing compounds, which are the hydrogenolysis products of structural fragments formed after destruction of kerogen and high-molecular components of oil. The gas chromatography–mass spectroscopy (GC–MS) method was applied to present the changes in the composition of mono- and dibenzothiophenes, which indicate conversion of heavy components into lighter aromatic hydrocarbons. The specific features of transforming trace elements in rock samples, asphaltenes, and carbene–carboids were observed by using the isotopic mass-spectrometry method.

Geochemical Assessment of the Biodegradation Levels of Some Crude Oils from Bayelsa State, Nigeria

Coastal swamp crude oil samples obtained from Clough creek, Azuzuama and Tebidaba oil fields were analyzed to obtain their biodegradation rankings. The studied samples were fractionated by column chromatography into saturated and aromatic hydrocarbons. The saturated hydrocarbons were analyzed using Gas Chromatography-Mass Spectrometry (GC-MS). Some diagnostic ratios such as C 30 αβhopane/(Pr+Ph), (Pr+Ph)/(nC 17 +nC 18 ) and C 29 αβ 25 norhopane/C 30 αβhopane were used in assessing the biodegradation rankings. Though biodegradation was evident in the studied samples, their individual levels were compared based on these ratios. Assessment of the crude oil samples using C 29 αβ25norhopane/C 30 αβhopane ratio show that the oils from AZU ST and TEB12 are more degraded when compared to oils from WELL 2. Consequently, (Pr+Ph)/ (nC 17 +nC 18) ratios show that TEB 12 is the most degraded while WELL 2 is the least degraded. AZU ST was also shown as the most degraded oil using C 30 αβhopane/(Pr+Ph) diagnostic ratio.

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

Ligands are innocent when they allow oxidation states of the central atoms to be defined. A noninnocent (or redox) ligand is a ligand in a metal complex where the oxidation state is not clear. Dioxygen can be a noninnocent species, since it exists in two oxidation states, i.e., superoxide (O2−) and peroxide (O22−). This review is devoted to oxidations of C–H compounds (saturated and aromatic hydrocarbons) and alcohols with peroxides (hydrogen peroxide, tert-butyl hydroperoxide) catalyzed by complexes of transition and nontransition metals containing innocent and noninnocent ligands. In many cases, the oxidation is induced by hydroxyl radicals. The mechanisms of the formation of hydroxyl radicals from H2O2 under the action of transition (iron, copper, vanadium, rhenium, etc.) and nontransition (aluminum, gallium, bismuth, etc.) metal ions are discussed. It has been demonstrated that the participation of the second hydrogen peroxide molecule leads to the rapture of O–O bond, and, as a result, to the facilitation of hydroxyl radical generation. The oxidation of alkanes induced by hydroxyl radicals leads to the formation of relatively unstable alkyl hydroperoxides. The data on regioselectivity in alkane oxidation allowed us to identify an oxidizing species generated in the decomposition of hydrogen peroxide: (hydroxyl radical or another species). The values of the ratio-of-rate constants of the interaction between an oxidizing species and solvent acetonitrile or alkane gives either the kinetic support for the nature of the oxidizing species or establishes the mechanism of the induction of oxidation catalyzed by a concrete compound. In the case of a bulky catalyst molecule, the ratio of hydroxyl radical attack rates upon the acetonitrile molecule and alkane becomes higher. This can be expanded if we assume that the reactions of hydroxyl radicals occur in a cavity inside a voluminous catalyst molecule, where the ratio of the local concentrations of acetonitrile and alkane is higher than in the whole reaction volume. The works of the authors of this review in this field are described in more detail herein.