Search

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 this research, combustion behaviour of three crude oils with different °API gravities was analysed. The thermogravimetric analyser (TGA) and differential scanning calorimeter (DSC) experiments were performed using three different heating rates (2, 5, and 10 °C min−1) under air atmosphere. The reaction regions, burn-out temperatures, and peak temperatures were determined accordingly. Two main reaction regions, particularly the low-temperature oxidation (LTO) and high-temperature oxidation (HTO) reactions, were figured out in TGA and DSC curves, which suggested exothermic behaviour. Kinetic parameters of the crude oils were determined using model free methods (Ozawa–Flynn–Wall, OFW, and Kissinger–Akahira–Sunose, KAS), which allows the calculation of kinetic properties at progressive conversion degrees without the requirement of any reaction models and f(α) estimations. The variation in activation energy with respect to the conversion degree pointed out that the LTO reaction stage can be subdivided into three subzones. The results indicated that the activation energies were changing depending on the conversion degree, which is an indication of complex reaction mechanisms. The change in activation energy with respect to conversion degree showed slight variation for heavy crude oil compared with that in light crude oil. [ABSTRACT FROM AUTHOR]

This paper discusses aquathermolysis process of heavy crude oil from Boca de Jaruco reservoir, which is developed by CSS method. The catalysts based on cobalt, nickel, iron and cupper are used to intensify the in-situ conversion processes. The active form of catalysts generates after steam injection. In second part of work the conversion of aromatic hydrocarbons depending on thermo-catalytic conditions and composition of catalysts are investigated. The thermo-catalytic treatment destructs resin and asphaltene molecules. The destruction products transform into aromatic fractions. The correlation between the C4-phenanthrene/naphtabenzothiophen ratio and the yields of aromatics and resins are revealed. The increase in high-molecular aromatic hydrocarbon, particularly tetramethyl-phenanthrene content is observed. However, the content of heteroatom compounds such as naphtabenzothiophen is constant. Based on IR-spectroscopy, the changes in composition of aromatic fraction are revealed. The lowest value of aromaticity index is detected for experiments with only hydrogen donor (without catalysts) and for experiments with Ni-, Cu-based catalysts. [ABSTRACT FROM AUTHOR]

This paper discusses aquathermolysis process of heavy crude oil from Boca de Jaruco reservoir, which is developed by CSS method. The catalysts based on cobalt, nickel, iron and cupper are used to intensify the in-situ conversion processes. The active form of catalysts generates after steam injection. The third part of paper discusses conversion of resins and asphaltenes. The influence of thermo-catalytic conditions and composition of catalysts are also studied. The destruction of resins and asphaltenes are observed after thermocatalytic treatments. The changes in composition of resins and asphaltenes are revealed by IR-spectroscopy data. [ABSTRACT FROM AUTHOR]

This paper is devoted to the study of aquathermolysis processes of heavy oil produced by CSS technology on Boca de Jaruco oil field. Various catalysts based on cobalt, nickel, iron and copper were used for intensification of in-situ upgrading processes of heavy oil. The first paper in series is presented results of transformation of crude oil and its saturate fraction after thermal treatment with and without catalysts by SARA analysis, MALDI mass-spectrometry, FTIR-spectroscopy and gas chromatography. It is revealed, that catalysts provide more deep conversion of asphaltenes and resins into lighter hydrocarbons. Particularly, for the given heavy oil, catalysts based on iron and nickel organic salts are more effective to reduce the content of high molecular weight components (asphaltenes). Saturates fraction after thermal treatment in presence of the catalysts is enriched with lighter alkanes in comparison to the crude oil treated without catalysts. Obtained results show that crude oil recovered by catalytic aquathermolysis processes will be better quality than the original oil in the place. [ABSTRACT FROM AUTHOR]

Aluminum oxides and hydroxides are widely applied because of the great variety of their modifications. In particular, aluminum oxides and hydroxides are used in petrochemistry and oil refining. However, amorphous aluminum compounds have not been sufficiently studied due to the complexity of their synthesis and the problems encountered during their study. The study of amorphous aluminum compounds is hindered by the ambiguity of terminology. In this work, the structures of amorphous aluminum compounds prepared by different methods and the properties that determine their applications have been highlighted in detail. Amorphous aluminum compounds play both positive and negative roles in petrochemistry; however, in petroleum refining, amorphous compounds (without promoters and transition metal salts) demonstrate a promising catalytic performance in oil upgrading. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This paper investigates aquathermolysis of heavy oil in carbonate reservoir rocks from Boca de Jaruco, which is developed by the cyclic steam stimulation method. The nickel-based catalyst precursor was introduced in order to intensify the conversion processes of heavy oil components. The active form of such catalysts—nickel sulfides—are achieved after steam treatment of crude oil at reservoir conditions. The experiments were carried out on a rock sample extracted from the depth of 1900 m. Changes in composition and structure of heavy oil after the conversion were identified using SARA-analysis, Gas Chromatography-Mass Spectroscopy of saturated fractions, FTIR spectroscopy of saturated fractions, and MALDI of resins. It is revealed that catalyst particles provide a reduction in the content of resins and asphaltenes due to the destruction of carbon-heteroatom bonds. Moreover, the destruction of C=Carom. bonds and interactions with aromatic rings are heightened. In contrast, the results of experiments in the absence of catalysts exposed polymerization and condensation of aromatic rings. The most remarkable result to emerge from the thermo-catalytic influence is the irreversible viscosity reduction of produced crude oil enhancing the oil recovery factor. Moreover, the introduction of catalysts increases the gas factor due to additional gas generation as a result of aquathermolysis reactions. The yield of methane gas is significantly high in the experimental runs with oil-saturated rocks rather than crude oil experiments. The gas factor reaches 45 m3/ton. [ABSTRACT FROM AUTHOR]

In this research, four different crude oils from Tatarstan oil fields with wide range of API gravities (from 16.6 to 32.5 °API) were used for hydrogen and carbon nuclear magnetic resonance spectroscopy (H NMR and C NMR) determinations. The hydrogen and carbon aromaticity factors were calculated by using the results of H NMR and C NMR spectroscopy results. The results show that the aromaticity factors were high for heavy crude oils. For predicting SARA fractions, the correlations were developed as a function of aromaticity factors. The developed correlations showed high accuracy for predicting SARA fractions for four crude oils. • The hydrogen and carbon aromaticity factors are increasing with increasing crude oil gravity. • The developed correlations showed high accuracy for predicting SARA fractions for four crude oils. • The maximum error was around 9.4% while the minimum was 0.1% for the developed correlations. [ABSTRACT FROM AUTHOR]

Abstract In this research, pressurized differential scanning calorimeter (PDSC) were used to estimate the thermal and kinetic behaviour of two different crude oils from Tatarstan oil fields under three different pressures (100, 600, 2000 kPa) at a constant heating rate (10 °C/min). The heat flow curves of both crude oils indicated two reaction regions known as low temperature oxidation (LTO) and high temperature oxidation (HTO). The reaction intervals were shifted to lower temperature regions with the increase in pressure. The activation energies were calculated according to Borchardt & Daniels and Roger & Morris methods and it was observed that the activation energies were decreasing at elevated pressures. Highlights • The PDSC curves of light and heavy crude oil showed two reaction regions, which are LTO and HTO. • The heat of reaction and heat flow values were increasing with increase in pressure. • Increase in pressure resulted in decrease in activation energy for both heavy and light crude oils. [ABSTRACT FROM AUTHOR]

In present work oxidation of two heavy oils in limestone matrix was studied using simultaneous thermogravimetry (TGA), derivative thermogravimetry (DTG) and FTIR-spectroscopy techniques in the temperature range from 25 to 900 °C. Before the measurements, the composition and properties of crude oils and limestone were evaluated. Obtained TG and DTG curves shows four different reaction regions: low temperature oxidation (LTO), fuel deposition (FD), high temperature oxidation (HTO) and decomposition of limestone. LTO reactions were accompanied by evaporation of light hydrocarbons, which was confirmed by appearance of stretching vibration bands of C-H groups in FTIR-spectra of evolved gases. Formation of carbon dioxide was observed for all oxidation reaction regions according to spectroscopic data. At the same time, CO was formed only in HTO region for both studied crude oils. Despite the different composition two crude oils have practically the same reactions intervals and peak temperatures. However, crude oil with higher API-gravity has a greater mass loss at the LTO and evaporation regions. The conversion of heavier oil with higher content of asphaltenes is larger during the high-temperature oxidation step. Three different kinetic models (Arrhenius, Coats & Redfern and Ingraham & Marrier) were used for analysis of TGA-DTG curves in LTO and HTO regions. Activation energy values of the crude oil samples were varied between 6.9–10.6 kJ/mol in low temperature oxidation and 91.8-.0–181.9 kJ/mol in high temperature oxidation regions. For two crude oils activation energies are similar in low temperature oxidation region. In high temperature oxidation region, crude oil with higher content of asphaltenes has larger activation energy. [ABSTRACT FROM AUTHOR]

The ramped temperature oxidation experiments were performed on heavy and light crude oil samples using the TGA and DSC instruments. The crude oils were mixed with different weight percentages (10%, 20%, and 30%) of water, as a result of which six different water-oil mixtures were prepared. The samples were heated up to 800 °C with three heating rates 20, 25, 30 °C/min. Two reaction regions, particularly the low temperature oxidation (LTO) and high temperature oxidation (HTO), were identified in TGA and DSC results. The LTO region can be divided into two subzones as before and after around 150 °C. In the first subzone, up to around 150 °C, the endothermic distillation process took place. The results showed that light crude oil and its mixtures had lower reaction starting and ending temperatures, and peak temperatures compared to heavy crude oil and its mixtures. As the water amount in the mixtures were increased, the reaction and peak temperatures shifted to lower temperatures. The kinetic analysis was also performed applying the Ozawa-Flynn-Wall (OFW), Kissenger-Akahira-Sunose (KAS), and ASTM kinetic methods. The activation energies and Arrhenius constants based on the TGA and DSC results were calculated accordingly. The light crude oil and its water mixtures had lower activation energy and Arrhenius constants compared to heavy crude oil and its mixtures. As the amount of water in the mixture was increased, the activation energy and Arrhenius constant decreased, which indicated that the presence of water in the crude oil increases its ability to combust more efficiently. • The crude oils and their water mixtures suggested two reaction regions, particularly the low temperature oxidation (LTO) and high temperature oxidation (HTO) regions. • The reaction temperatures of heavy crude oil mixture were higher compared to that of light crude oil mixture. • Presence of water in the crude oil makes it vulnerable to combustion, which increases the combustion efficiency. [ABSTRACT FROM AUTHOR]

• Catalysts promoted the hydrogenolysis of resins and asphaltenes. • The bimetallic catalyst based on nickel and iron metals with the mass ratio of 1:1 exhibits the best catalytic performance. • Hydrothermal treatment of heavy oil in the presence of bimetallic nanoparticles significantly reduced its viscosity. • The destruction products of asphaltene fragments were observed by GC–MS in the composition of saturates and aromatics. • The content of asphaltenes decreases with the increase of iron metal concentration in the composition of the bimetallic catalyst. This paper examines the transformation of heavy oil composition in porous media of carbonate reservoir rocks under hydrothermal processes in the presence of transition metal sulfides, which form in-situ from the organic-soluble precursors. It was revealed that catalysts significantly promoted the destruction of asphaltenes. Its content was reduced from 15 wt.% to 12 wt.% in the presence of iron-based catalyst. The bimetallic catalyst based on nickel and iron with the mass ratio of 1:1 exhibited the best performance in terms of reducing heavy oil viscosity. Combination of two different metals allowed to involve the wide ranges of carbon-heteroatom bonds, which are mainly concentrated in resins and asphaltenes, into the hydrogenolysis reactions. Irreversible reduction of heavy oil viscosity in-place not only eases the further downstream processes such as pipeline transportation and refinery, but also decreases carbon footprints of the produced oil owing to the increase in the intensity of hydrogenation processes. [Display omitted] [ABSTRACT FROM AUTHOR]

In this study a new, fast and simple method based on low field NMR-relaxometry for in-situ determination of SARA (saturates, aromatics, resins and asphaltenes) composition of crude oils was proposed. This method was tested on 22 samples of crude oils with a wide range of SARA-composition and API gravity values (4.6–42.0°), including extra-heavy, heavy, medium and light crude oils. Results obtained by low-field nuclear magnetic resonance (LF-NMR) were compared with conventional SARA analysis method (ASTM D 4124). Comparison shows good coincidence between SARA values determined by LF-NMR and conventional method data for heavy fractions of asphaltenes and resins (R2 is equal to 0.98 and 0.91, respectively) and for the sum of light fractions including saturates and aromatics (R2 = 0.96). However, comparison for saturated and aromatic compounds separately gave low correlation coefficients (R2 ≤ 0.61 and 0.27, respectively) and relatively soaring standard deviation for individual correlations for saturates and aromatics (8.18 and 9.20). Consequently, LF- NMR relaxation as an alternative method for studying the composition of crude oil allows the determination of asphaltenes, resins and the sum of light fractions (saturates and aromatics) without their extraction (in-situ), which greatly simplifies and accelerates conventional chromatographic analysis. This method can be successfully applied for different types of crude oils with a wide range of API gravity and viscosity values. Image 1 • 22 crude oils were investigated using low-field nuclear magnetic resonance (LF-NMR) and SARA analysis techniques. • SARA composition data of oil samples was obtained by means of traditional SARA separation and LF-NMR relaxation data. • T2 relaxation curves for measured oil samples were obtained. • Protons T2 relaxation times of SARA fractions in studied oil samples were obtained. • Good correspondence between two methods was observed for resins, asphaltenes and the sum of saturates and aromatics fractions [ABSTRACT FROM AUTHOR]

• Role of water in aquathermolysis was investigated by isotope tracing technique. • Chemical role of water as a green and environmental hydrogen-donor was proved. • Significant deuterium exchanges in aliphatic and aromatics parts observed in FTIR. • Isotope analysis shows deuterium substitution in upgraded oil and SARA fractions. • Ni-tallate promoted both the donating capacity of water and upgrading performance. The goal of this work is to try to figure out the role of water in catalytic and non-catalytic aquathermolysis by using isotope tracing techniques. For this purpose, heavy water (deuterium oxide, D 2 O) was used to replace the ordinary water (H 2 O) for catalytic and non-catalytic aquathermolysis processes of extra-heavy oil with high sulfur content in autoclave. The donating and upgrading performance of D 2 O were deeply investigated by analyzing the upgraded (deuterated) oil and their SARA (saturates, aromatics, resins and asphaltenes) fractions using different tracing techniques (FTIR, isotope and elemental analysis), evolved gases by GC, and change in physical-chemical properties of upgraded (deuterated) oils by viscosity measurement, SARA analysis, elemental analysis and GC, etc. The results proved the chemical role of water as a green and environmental hydrogen-donor solvent during aquathermolysis process, verified by considerable deuterium substitution (deuteration) obtained from isotope analysis both in upgraded oil and SARA fractions. The results are further supported by significant deuterium exchanges (deuteration) of aliphatic and aromatics parts in the initial and deuterated oil samples and their individual SARA fractions in FTIR spectra. Simultaneously, introducing Ni-tallate as an oil-soluble catalyst promoted the donating capacity of water, thus significantly improving the upgrading performance. The important finding about the role of water in catalytic and non-catalytic aquathermolysis not only enriches the theoretical basis in this area, but also provides a strong support for the use of catalysts in aquathermolysis for improving in-situ heavy oil upgrading performance. [ABSTRACT FROM AUTHOR]