What Is The Mixture Of Petroleum? – Incompatibility with fine pyrite and organic matter in turbid waters. scanning electron microscopy and large-scale image analysis
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What Is The Mixture Of Petroleum?
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Received: 15 March 2020 / Revised: 2 April 2020 / Accepted: 13 April 2020 / Published: 16 April 2020
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The commercial discovery of huge crude oil deposits at depths of 10 km in various oil basins around the world casts doubt on the validity of theoretical calculations that determined that the main oil production zone is located at a depth of 6-8 km (oil “window”. However, the behavior of complex of hydrocarbon systems in thermal conditions corresponding to depths below 6-8 km is poorly known. We experimentally investigated the thermal stability of a complex hydrocarbon system under conditions of pressure and temperature of the lower Earth’s crust using Raman and Mossbauer spectroscopy. Our results showed the chemical stability of a complex hydrocarbon system in thermal conditions relevant to depths of 50 km, including the redox stability of hydrocarbon systems in a highly oxidizing environment. The results of these experiments allowed us to revise the depth range where oil deposits can occur.
During the last few decades, huge ultra-deep oil fields have been discovered in various oil basins in the world at a depth greater than 10 km [1, 2, 3]. These deposits are located below the main oil production zone, which is traditionally called the “oil window” and usually occurs at a depth of 6-8 km [4, 5, 6]. Many efforts have been made to study the thermal evolution of organic compounds and petroleum, especially in the Earth’s crust. Until the early 1990s, most studies concluded that only natural gas deposits could be found at depths with temperatures above 170-180 °C. These conclusions are based on the theoretical approach developed by Tissot and Espitalie . The commercial discovery of gas condensate deposits with temperatures around 200 °C (for example, the Elgin and Franklin fields located in the Central Graben area of the North Sea basin) [8, 9] cast doubt on the validity of the above theory. . calculations.
In theoretical modeling , the high pressure factor was taken into account and it was shown that crude oil can be stable at temperatures up to 240–260 °C, and thermal cracking of crude oil into gas is not possible. under reasonable watershed conditions.
The results of an experimental study of the thermal stability and decomposition of individual hydrocarbons at temperatures up to 450 °C are presented in the literature [11, 12, 13]. In another study, experiments were conducted under a pressure of 70 MPa at a temperature of up to 330 °C . One of the main conclusions from the aforementioned experimental results can be summarized as follows. the thermal stability of individual hydrocarbons differs greatly from the thermal stability of the same hydrocarbons in a mixture.
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In our study, we investigated the thermal stability of a petroleum system model under pressures of 0.7–1.4 GPa and temperatures of 320–450 °C. These thermobaric conditions corresponded to a depth of 20–50 km. Furthermore, we investigated the possible influence of the oxidized environment of the lower crust on the stability of hydrocarbons. This appears to be appropriate when modeling deep conditions . This paper provided a detailed description of the experimental procedure and results that confirmed the thermal stability of complex hydrocarbon systems at a depth of 50 km.
Symmetric DACs of the BKS90 type (diamond anvil cells) with 250 μm diameter cuvettes were used in all experiments. A pre-impregnated steel gasket (thickness 250 μm) with a hole (diameter 125 μm) was prepared as a sample chamber. The cavity is filled with a synthetic hydrocarbon mixture, and Sm:IAG and ruby chips are placed inside the cell. A liquid hydrocarbon mixture also served as a pressurized medium. Pressure and temperature were measured with Sm:IAG and ruby wavelength shift [16, 17] using Raman spectroscopy (He-Ne laser wavelength 514.5 nm and power 0.001–0.6 V). For additional temperature control, a Pt/Pt-Rh (10%) thermocouple was used in the DAC (the thermocouple contacted the diamond side and gasket for efficient heat transfer (Supplementary Materials, Fig. S1)).
A Pt heater with heat-resistant adhesive was placed inside the cell, which also served as insulation for the Pt wire and thermocouple. The temperature increased at a rate of 50–60 °C/h according to thermocouple data. Several times per hour, the temperature and pressure in the sample were measured by changing the Raman wavelength. The pressure inside the specimen was kept constant by using DAC screws to fix it. After reaching the required temperature, it was maintained during exposure (pressure and temperature in the sample were checked 2-3 times per hour during exposure). The exposure time varies from 3 to 12 hours. The heating was then stopped and the sample was quenched (the pressure inside the cell was monitored and kept constant). The sample in the DAC was analyzed under pressure using Raman spectroscopy before heating the sample and after cooling the sample.
Add to the sample chamber. The DAC design was the same as the previous experiments, except that a rhenium spacer (250 μm thick) was used for Mössbauer spectroscopy in this experiment. Conventional Mossbauer spectroscope a
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A contact source was used at the Baierisches Geoinstitut, Baireuth University (BGI) as a diagnostic method for the detection of new iron compounds after heating. Mössbauer spectra of the sample were collected before heating and after cooling at the same pressure. Raman spectroscopy was not used for hydrocarbon analysis in this series of experiments because Fe
A natural sample of Astrakhan oil from the Korchaginsky field (see Supplementary Materials, Table S1 for more details) and an artificially synthesized hydrocarbon mixture (Supplementary Materials, Figure S2, Table S2) were used in the experiments. The composition of the hydrocarbon mixture was obtained by processing the gas chromatogram of the hydrocarbon system. The volumetric concentration of each individual component was calculated as the ratio of the area under the corresponding peak to the total area under all peaks in the chromatogram.
Experiments were performed in diamond anvil cells (DAC) with resistance heating and in situ Raman spectroscopic analysis (see Methods section for details). The use of natural oil as the main source of the test sample was a problem due to the high luminescence in the Raman spectrum (Figure 1a), which is a consequence of the presence of asphaltene compounds in natural crude oil. Therefore, an artificially synthesized mixture of hydrocarbons similar to natural gas-condensate with a known quantitative and qualitative composition was used in the tests. This synthetic hydrocarbon system had clear Raman spectra without luminescence (Figure 1b).
To investigate the thermal stability of the model hydrocarbon system, three series of experiments were conducted at different exposure times at temperatures of 320–450 °C and pressures of 0.7–1.4 GPa ( Table 1 ).
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The results of the experiments showed that the hydrocarbon mixture is thermally stable in these thermobaric conditions. The Raman spectra of the synthetic oil before and after heating are shown in Figure 2. The composition of the hydrocarbon mixture did not change during all three experiments. All representative hydrocarbon peaks in the spectrum retained their shape, Raman shift and intensity; no new peaks appeared after heating. In the third series, increasing the time of exposure to heating by 4 times (from 3 to 12 hours) did not affect the composition of the synthetic oil.
The next step in the research was to study the resistance of oil to oxidation in thermobaric conditions of the earth’s crust and the possibility of reaction with it.
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