Evaluation of the aquathermolysis catalyst effect on the composition and properties of high-viscosity oil from the Strelovskoe field

The article examines the aquathermolysis process of high viscosity oil from Strelovskoe field developed by RITEK LLC using steam injection. Laboratory modeling of non-catalytic and catalytic aquathermolysis in a high-pressure reactor was performed. Laboratory tests have demonstrated the high efficiency of the iron-based oil-soluble catalyst developed at Kazan Federal University in the destruction reactions of resinous asphaltenes. Samples of the initial oil as well as products of non-catalytic and catalytic aquathermolysis in the presence of iron tallate and the solvent Asphalt-Resin-Paraffin Deposits were studied at temperatures of 200, 250 and 300°C for 24 hours. In addition, the gas composition of the oil aquathermolysis products and the viscosity-temperature characteristics of the oil samples were determined. The studies have shown that catalytic aquathermolysis has a significant effect on the changes in the composition and properties of oil from the Strelovskoe field. It was found that the presence of a catalyst contributes to decarboxylation reactions, increases the degree of desulfurization and decreases the viscosity of oil samples. Keywords: high-viscosity oil; aquathermolysis; catalyst precursor; steam thermal treatment; viscosity.

Aquathermolysis of high-viscosity oil terrigenic sediments in the presence of iron oxide (II, III)

Nowadays, it is especially important and relevant to improve the efficiency of existing methods of enhanced oil recovery, in particular, thermal methods using water steam. The use of catalysis at the stage of development of unconventional hydrocarbon fields, namely super-viscous and bituminous oils, will allow solving this problem. This work is devoted to the study of the transformation of heavy oil from the Ashalchinskoye field in the process of catalytic aquathermolysis. The oil samples were extracts from sandstone, which was subjected to thermal steam treatment in a high-pressure reactor at temperatures of 200 and 250C for 24 h. Nanosized iron (II, III) oxide in complex with a hydrogen donor was used as a catalytic composition. According to the results of SARA-analysis, it was found that at a temperature of 200C, iron oxide does not show its catalytic properties, and there is no noticeable improvement in the composition of heavy oil. The destruction of resins and asphaltenes is observed after thermocatalytic treatment at 250C. This leads to the enrichment of oil with lighter hydrocarbons, which is confirmed by GC-MS data of the saturated fraction of oil. All this provides a significant decrease in the viscosity of heavy oil compared to the non-catalytic process from 1140 cP to 37 cP The formation of coke-like substances adsorbed on sandstone as a result of thermocatalytic action at 250C was revealed by the results of TG-DSC.

Enhanced aquathermolysis of extra-heavy oil by application of transition metal oxides submicro-particles in relation to steam injection processes

In order to investigate the catalytic effects of transition metal oxides submicro-particles on aquathermolysis of Liaohe extra-heavy crude oil, the catalysts NiO, α·Fe2O3 and Co3O4 are used and evaluated during the experiments. The optimum mass fraction of the catalyst and water was determined to be 5.0 wt% and 30 wt%, respectively. The optimum reaction time for aquathermolysis was 24 h, and the optimum reaction temperature was 240 °C. The analysis results showed the heavy oil was upgraded dramatically by addition of the catalysts based upon viscosity reduction, saturate/aromatics/resins/asphaltenes analyses, elemental analysis, Fourier transform infrared spectroscopy and gas chromatography. All results show the heavy oil is in situ updated dramatically by catalytic aquathermolysis under the optimum operating conditions. A five-lump model is proposed for estimating kinetic parameters of aquathermolysis and agrees well with the experimental data.

Transformation of Resinous Components of the Ashalcha Field Oil during Catalytic Aquathermolysis in the Presence of a Cobalt-Containing Catalyst Precursor

The aim of this work was to study the fractional composition of super-viscous oil resins from the Ashalcha field, as well as the catalytic aquathermolysis product in the presence of a cobalt-containing catalyst precursor and a hydrogen donor. The study was conducted at various durations of thermal steam exposure. In this regard, the work enabled the identification of the distribution of resin fractions. These fractions, obtained by liquid adsorption chromatography, were extracted with individual solvents and their binary mixtures in various ratios. The results of MALDI spectroscopy revealed a decrease in the molecular mass of all resin fractions after catalytic treatment, mainly with a hydrogen donor. However, the elemental analysis data indicated a decrease in the H/C ratio for resin fractions as a result of removing alkyl substituents in resins and asphaltenes. Moreover, the data of 1H NMR spectroscopy of resin fractions indicated an increase in the aliphatic hydrogen index during catalytic aquathermolysis at the high molecular parts of the resins R3 and R4. Finally, a structural group analysis was carried out in this study, and hypothetical structures of the initial oil resin molecules and aquathermolysis products were constructed as well.

Extra-Heavy Oil Aquathermolysis Using Nickel-Based Catalyst: Some Aspects of In-Situ Transformation of Catalyst Precursor

In the present work, we studied the catalytic performance of an oil-soluble nickel-based catalyst during aquathermolysis of oil-saturated crushed cores from Boca de Jaruco extra-heavy oil field. The decomposition of nickel tallate and some aspects of in-situ transformation of the given catalyst precursor under the steam injection conditions were investigated in a high-pressure batch reactor using XRD and SEM analysis methods. The changes in physical and chemical properties of core extracts after the catalytic aquathermolysis process with various duration were studied using gas chromatography for analyzing gas products, SARA analysis, GC-MS of saturated and aromatic fractions, FT-IR spectrometer, elemental analysis, and matrix-activated laser desorption/ionization (MALDI). The results showed that nickel tallate in the presence of oil-saturated crushed core under the injection of steam at 300 °C transforms mainly into nonstoichiometric forms of nickel sulfide. According to the SEM images, the size of nickel sulfide particles was in the range of 80–100 nm. The behavior of main catalytic aquathermolysis gas products such as CH4, CO2, H2S, and H2 depending on the duration of the process was analyzed. The catalytic upgrading at 300 °C provided decrease in the content of resins and asphaltenes, and increase in saturated hydrocarbon content. Moreover, the content of low-molecular alkanes, which were not detected before the catalytic aquathermolysis process, dramatically increased in saturates fraction after catalytic aquathermolysis reactions. In addition, the aromatics hydrocarbons saturated with high molecular weight polycyclic aromatic compounds—isomers of benzo(a)fluorine, which were initially concentrated in resins and asphaltenes. Nickel sulfide showed a good performance in desulfurization of high-molecular components of extra-heavy oil. The cracking of the weak C–S bonds, which mainly concentrated in resins and asphaltenes, ring-opening reactions, detachment of alkyl substitutes from asphaltenes and inhibition of polymerization reactions in the presence of catalytic complex reduced the average molecular mass of resins (from 871.7 to 523.3 a.m.u.) and asphaltenes (from 1572.7 to 1072.3 a.m.u.). Thus, nickel tallate is a promising catalyst to promote the in-situ upgrading of extra-heavy oil during steam injection techniques.

In-Situ Heavy Oil Aquathermolysis in the Presence of Nanodispersed Catalysts Based on Transition Metals

The aquathermolysis process is widely considered to be one of the most promising approaches of in-situ upgrading of heavy oil. It is well known that introduction of metal ions speeds up the aquathermolysis reactions. There are several types of catalysts such as dispersed (heterogeneous), water-soluble and oil soluble catalysts, among which oil-soluble catalysts are attracting considerable interest in terms of efficiency and industrial scale implementation. However, the rock minerals of reservoir rocks behave like catalysts; their influence is small in contrast to the introduced metal ions. It is believed that catalytic the aquathermolysis process initiates with the destruction of C-S bonds, which are very heat-sensitive and behave like a trigger for the following reactions such as ring opening, hydrogenation, reforming, water–gas shift and desulfurization reactions. Hence, the asphaltenes are hydrocracked and the viscosity of heavy oil is reduced significantly. Application of different hydrogen donors in combination with catalysts (catalytic complexes) provides a synergetic effect on viscosity reduction. The use of catalytic complexes in pilot and field tests showed the heavy oil viscosity reduction, increase in the content of light hydrocarbons and decrease in heavy fractions, as well as sulfur content. Hence, the catalytic aquathermolysis process as a distinct process can be applied as a successful method to enhance oil recovery. The objective of this study is to review all previously published lab scale and pilot experimental data, various reaction schemes and field observations on the in-situ catalytic aquathermolysis process.