D. N. Borisov

Features of the composition of vanadyl porphyrins in the crude extract of asphaltenes of heavy oil with high vanadium content

ABSTRACT Features of changes in the content of nickel and vanadium in heavy oils and their asphaltenes are shown for various fields of Volga-Ural region (Russia). The change in the content of vanadyl complexes in the studied asphaltenes upon increase of vanadium content was demonstrated. Several polar solvents (acetone, N,N-dimethylformamide, isopropanol, acetonitrile) are compared as extractants to obtain crude extracts of vanadyl porphyrins from asphaltenes with vanadium content of 0.44 wt%. The opportunity of more efficient extraction of vanadyl porphyrins from asphaltenes is shown by deposition extraction method, particularly when using N,N-dimethylformamide. Absorption spectra and matrix-assisted laser desorption/ionization (MALDI) mass spectra of the extracts obtained were analyzed. For extracts with maximum content of vanadyl porphyrins, the presence of mainly etio- and deoxophylloerythroetioporphyrins was revealed. It was shown that proportion of etio-type vanadyl porphyrins does not exceed 75% of the amount of porphyrins of DPEP-type. A maximum of molecular weight distribution in both types falls on a homologue of vanadyl porphyrin C31 containing nine carbon atoms in the alkyl substituents.

Concentrations of Vanadium and Nickel and Their Ratio in Heavy Oil Asphaltenes

Trends in the vanadium and nickel concentrations in asphaltenes of heavy oils from different oilfields, in which the total content of these metals vary from 0.0049 to 0.1795 wt %, have been studied. It has been shown that as the vanadium and nickel content in heavy oils increases, vanadium concentrates faster than nickel in asphaltenes. In heavy oils, asphaltenes contain approximately 40–90% of total vanadium and 25–75% of total nickel. The summed concentration of vanadium and nickel in heavy oil asphaltenes can reach 1 wt %.

Sulfuric Acid Assisted Extraction and Fractionation of Porphyrins From Heavy Petroleum Residuals With a High Content of Vanadium and Nickel

Primary porphyrin extracts were obtained from carbon tetrarchloride solutions of different heavy oil residuals with assistance of sulfuric acid. According to data of chromatographic separation of extracts porphyrinic fractions appear in amount of 13.0–24.2%. Based on UV/visible absorption spectroscopy the presence of porphyrins of etio and phyllo types mostly with rhodo and deoxophylloerythroetioporphyrins in lower amount was established. The content of porphyrins in obtained fractions was determined at the level of 15.3–44.8% of the total weight. It was shown that a higher concentration of porphyrins in sulfuric acid extracts occurs for the case of the high vanadium and nickel content and low amounts relation of asphaltenes to resins.

Differentiation of heavy oils according to the vanadium and nickel content in asphaltenes and resins

The features of the distribution of vanadium and nickel between asphaltenes and resins have been revealed using heavy oils from Tatarstan and Samara oblast oilfields as an example. It has been shown that depending on the V and Ni content in asphaltenes and resins, heavy oils of different productive plays are divided into two separate groups. An increase in the V or Ni content of heavy oils is accompanied by an increase in the concentration of the respective metal in asphaltenes and resins. The intervals of variation in the V and Ni content of asphaltenes and resins of the oils attributed to each group have been determined. As the V concentration in asphaltenes increases, the V/Ni ratio also increases, a feature that is not characteristic of resins.

Composition of the Products of Thermolysis of Heavy Oil with the Addition of Light Hydrocracked Naphtha

Abstract A series of experiments has been carried out on the thermolysis of heavy oil using 2.5–10.0% light hydrocarbon naphtha additive of vacuum gasoil prepared from conventional oil. It has been shown that the employment of the additive increases the conversion of heavy oil, avoids coke formation in the products of thermolysis as compared to the basic process without additive, and does not prevent the decrease in the viscosity of the products during thermolysis. It has been revealed on the example of the heavy oil of Ashal’chinskoe deposit (Russia) that the thermolysis with the addition of light naphtha gives a liquid product with the yield higher than 97% and the viscosity of less than 80 mm2/s.

Composition and Properties of Oxidation Products of Heavy Oil Resid Asphaltenes

Asphaltenes of various heavy oil resids are oxidized by aqueous sodium percarbonate solutions at 200°C and 4 MPa pressure. The composition and properties of the obtained products are analyzed. Water-soluble oxidation products in the asphaltene oxidation products comprise 47.4-49.4%. Products of oxidative condensation of asphaltenes enriched with hydroxyl, ether, and carboxyl groups dominate in the composition of water-insoluble oxidation products. The water-soluble oxidation products represent carboxylic acid concentrate. The characteristics of the structural-group composition of the obtained oxidation products are disclosed. The possibility of practical utilization of asphaltene oxidation products as adhesion additives to road asphalt and for removal of phenol from water is demonstrated.