Сверхкритические флюиды. Теория и практика
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2017, N3, pp. 03-19

O.N. Fedyaeva, V.R. Antipenko, A.A. Vostrikov

Composition of Oil Fractions Obtained in Conjugated Processes of Heavy Sulfur-Rich Oil Thermolysis and Activated Carbon Oxidation by Supercritical Water-Oxygen Fluid

The composition of oily fractions (OFs) obtained at the heavy sulfur-rich oil conversion is studied by means of physical and chemical methods of analysis. The oil was supplied from the top into the vertical tubular reactor packed with activated carbon (AC), where supercritical water-oxygen fluid was pumped from the bottom through the AC bed. The experiment was performed at 30 MPa, temperature of upper, middle and bottom parts of the reactor equal to 673, 723 and 723 K, variable flow rate of oxygen (0—3.5 g/min) and constant flow rate of oil and water (4 and 6 g/min, respectively). Based on the temporal trends in the reactor wall temperature and the power of resistance heaters it is revealed that due to heat generation during the combustion of oil high-molecular components, accumulated in the AC bed, the conversion process occurs in autothermal mode. The movement of the combustion front along the reactor axis is detected. It is shown that isoprenoids and normal alkanes, 1-alkyl-2,3,6- trimethylbenzenes, alkyl-derivatives of benzo- and dibenzothiophenes are the main components of the crude oil OF. The yield of OFs, whose portion in the liquid products exceeds 90 %, has an extreme dependence on the oxygen flow rate. As the latter increases and the temperature of the reaction mixture rises due to a heat generation upon combustion, the relative content of bi- and tricyclic aromatic hydrocarbons alkylderivatives, as well as benzo- and dibenzothiophenes in the OFs of conversion products increases too. The content of fractions boiling at T < 493 K in the OFs of the conversion product increases by 2—3 times compared to the crude oil OF.

Key words: heavy oil, supercritical water-oxygen fluid, activated carbon, oxidation, heat release

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