Analysis of hydrocarbons stability under thermobaric conditions … · 1 –sample spectra before...
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Aleksandr Serovaiskii, A. Kolesnikov, V. Kutcherov Gubkin Russian State University of oil and gas, KTH Royal Institute of Technology e-mail: [email protected] Biogenic petroleum origin theory Abiogenic petroleum origin theory Analysis of hydrocarbons stability under thermobaric conditions of the Earth crust and the upper mantle Formation of natural-gas-like hydrocarbons mixture from inorganic substances or from individual hydrocarbons under conditions of the upper mantle had restarted discussions on the problem of petroleum formation and hydrocarbons properties in general. While individual hydrocarbon compounds under pressure were studied already to a certain extent, raw natural petroleum had never been loaded in diamond anvil cell or big press but two published works devoted to thermal conductivity measurement. The purpose of my research was to find main thermobaric regularities of petroleum behavior: temperatures and pressures of vitrification, crystallization, possible chemical changes like cracking, dissociation or condensation. Crude oil stability was investigated in the earth crust thermobaric conditions (up to 450ºC and 1,5 GPa) and upper mantle thermobaric conditions (up to 1000ºC and 5,5 GPa). The result of the experiments showed that crude oil could save its stability in such conditions. The crude oil deposits can be situated much deeper in the earth crust than the organic oil and gas origin theory claims. Some possible reactions of crude oil and iron compounds in upper mantle conditions were modeled and carried out (up to 2000+ºC, up to 10 GPa). Iron carbides and hydrides were obtained. These substances may take part in deep carbon and hydrogen cycle. Abstract Petroleum stability in the Earth crust Fig.2. Object – Fischer - Tropsh synthetic oil ( received from Dr. K.G. Ione ( Zeosit Co.) chromatogram toluols, xylols alkanes to C9 arenes C11+ 320 °C 0,7 GPa, 3 hours heating (20-30 km) 1 – sample spectra before heating 2 – sample spectra after heating 420 °C 1,2 GPa, 3 hours heating (30-45 km) 450 °C 1,4 GPa, 12 hours heating (35-50 km) Fig. 4. Experiments result The theory of biogenic petroleum origin claims that there is a “crude oil window” – the range of depth in the Earth crust, where crude oil deposits may occur. It should be no oil deposits deeper than this “oil window” level, only gas deposits. In deeper conditions crude oil will be cracked. But such deep crude oil deposits were found. They are explored successfully in industrial purposes. So the main goal of the experiment was to check till what depth crude oil can keep its stability. The investigations were made in Diamond Anvil Cells (DAC). The main goal was to investigate the petroleum stability in TP conditions corresponding to the Earth crust. Crude oil showed high luminescence in Raman spectroscopy (Fig.1), so it was impossible to see any picks on the spectra. To solve this problem the synthetic oil was taken as an experiment sample (Fig.2). It was a mixture of hydrocarbons with known composition similar to gas condensate (very light oil). To heat the sample the resistive heating was used. To control pressure and temperature Ruby and Sm:YAG were used[1,2], the thermocouple was used for additional temperature control (Fig.3). The temperature range was 320 - 450 °C, the pressure range was 0,7 - 1,4 GPa (up to 50 km depth). It was carried out three experiments to investigate the petroleum stability in the Earth crust TP conditions - P=0,7 GPa, T=320 °C (20-30 km), 3 hours; P=1,2 GPa, T=420 °C (30-45 km), 3 hours; P=1,4 GPa, T=450 °C (35-50 km), 12 hours. The experimental result showed sample stability in such TP conditions (Fig.4). The Raman spectra of the sample after heating was the same as the Raman spectra before heating. Diamond picks HC picks HC picks Diamond picks HC picks HC picks Diamond picks HC picks HC picks Diamond picks HC picks HC picks Diamond picks HC picks HC picks Diamond picks HC picks HC picks Fig.1. Raman spectra of crude oil (Astrakhan deposit) at different pressures Fig.3. DAC with resistive heater and thermocouple In 1877 the Russian chemist Dmitry Mendeleev published a hypothesis that received a name of carbide theory of petroleum formation: 1) there is iron in the Earth’s interior, 2) at least partially it is in the reduced state and in the compounds with carbon, 3) water can reach metal (mostly iron) carbides and form petroleum [3,4,5]. This hypothesis lost its power when petroleum composition was more thoroughly investigated and compared with products of carbide-water reactions. While formation of petroleum from carbides in Earth’s interiors and its migration upwards is arguable, important role of hydrocarbon fluids in subducting slabs became evident recently. Oceanic lithosphere together with petroleum deposits located both in sediment layer and basement rocks is transferred into the Earth by subduction [6]. To get information about possible transformations of iron compounds in the subducting slab petroleum-ferropericlase ((Mg,Fe)O) system was investigated in the range of thermobaric conditions corresponding with the depth up to 280 km. The initial sample assemblage consisting of a thin foil of 99% 57 Fe-enriched ferropericlase with 20 % 57 FeO and crude oil was loaded in DAC. Double-side heating with optical fiber-based lasers (50W and 100W) was used to produce temperatures that were measured by means of multi-wavelength spectroradiometry (Fig.1). Mossbauer’s spectroscopy was used for sample analysis. Two series of experiment were held – at 6,9 GPa and 9,5 GPa. The first heating was at 1000°C(100) during 5 minutes. After the first heating the cell was cooled and the Mossbauer’s spectra was made. After that the cell was heated the second time at 1500°C(100). Then the cell was cooled and the Mossbauer’s spectra was made. The results of the experiments are shown on the Fig.2. At 6,9 GPa and 1500°C iron hydride was generated, at 9,5 GPa and 1500°C iron hydride and iron carbide were generated [7,8]. If formation of carbides and hydrides is possible, then may be pressure will significantly change the composition of hydrocarbons mixtures producing from carbide-water interaction? Probably Mendeleev was not so wrong? Observation of carbides formation from natural petroleum and ferropericlase in mantle modeling materials let us to suggest existence of these substances in real geological conditions. On the depth of 200-210 km in the presence of FeO iron hydrides (FeH) is formed. In the deeper zone (depth of 280-290 km) the mixture of iron hydride (FeH) and iron carbide-cohenite (Fe 3 C) could be observed.) Our results identify novel mechanisms that can lead to one of the possible carbon cycle: hydrocarbons- iron hydrides and carbides formation-hydrocarbons. Carbides and hydrides from petroleum. Mendeleev’s carbide theory reverse? “The War” of Petroleum generation paradigms Hydrocarbons are generated in upper mantle layer from donors of carbon and hydrogen in extreme thermobaric conditions. Deep fluid goes up through migration channels and formats crude oil and natural gas deposits in Earth crust. Tiny sea plants and animals died and were buried on the ocean floor. Over time, they were covered by layers of sediment and rock. Over millions of years, the remains were buried deeper and deeper. The enormous heat and pressure turned them into oil and gas. Fig.1. The laser heating unit with DAC Fig.2. Results of the laser heating experiments What theory is right in this dispute? How was petroleum generated on our planet and how did it occur in the Earth crust? Conclusions 1. Petroleum can be stable at the Earth crust TP conditions up to 50 km depth (450°C, 1,4 GPa, at least during the experimental time). We can suggest that deep crude oil deposits may occur in the Earth crust (deeper than 10 km). 2. Iron carbide and iron hydride can be generated from crude oil and FeO and exist at upper mantle TP conditions (up to 280 km). Our results identify novel mechanisms that can lead to one of the possible carbon cycle: hydrocarbons-iron hydrides and carbides formation-hydrocarbons. Future plans 1. To find the thermobaric conditions limit of hydrocarbons stability. 2. To investigate a new analysis method that can be applied for crude oil sample. 3. To investigate petroleum stability in the porous rock at thermobaric conditions corresponding to the Earth crust and upper mantle. 4. To make an experiment with iron carbide, iron hydride and water at TP conditions corresponding to the Earth crust and upper mantle. 5. To investigate the possible mechanisms of petroleum chemical reactions at TP conditions corresponding to the Earth crust and upper mantle. What is petroleum? "Petroleum is a complex mixture of naturally occurring hydrocarbon compounds found in rock. Petroleum can range from solid to gas, but the term is generally used to refer to liquid crude oil” (Schlumberger Oilfield Glossary) Exploration Transportation Refining 1. D. Trots et al., High-temperature structural behaviors of anhydrous wadsleyite and forsterite, American Mineralogist, Volume 97, 2012, pages 1582–1590 2. H.K. Mao et al., Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions, Journal of geophysical research, vol.91, NO 5, 1986, p. 4673-4676 3. Zhurnal Russkogo Himicheskogo I Fizicheskogo Obschestva pri imperatorskom S.-Peterburgskom universitete, V.9, N.2, sec.1, 1877, p. 36-37 4. Mendeleev, D., L'Origine du pétrole. Revue Scientifique, 2e Ser., VIII, 1877, p. 409-416 5. Set of D.I. Mendeleev works, Izdatelstvo Akademii Nauk SSR, Leningrad-Moscow, 1949, V.10, p. 228-244 6. D. A. Sverjensky at al., Important role for organic carbon in subduction-zone fluids in the deep carbon cycle, Nature Geoscience, published online: 17 November 2014, DOI: 10.1038/NGEO2291 7. O. Narygina et al., X-ray diffraction and Mössbauer spectroscopy study of fcc iron gydride FeH at high pressures and implications for the composition of the Earth's core, Earth and Planetary Science Letters, 307, 2011, p. 409–414 8. C. Prescher et al., Structurally hidden magnetic transitions in Fe 3 C at high pressures, Physical review, B 85, 140402(R), 2012 Literature Before heating After the first heating, 1000°C After the second heating, 1500°C 6,9 GPa 9,5 GPa FeO α-Fe (11%) FeH (27%) FeH (34%) FeH (24%) Fe 3 C (36%) FeO (28%) FeO FeO FeO FeO (40%) https://wsc11sci.wikispaces.com/Carbon+Based+Fuels
Transcript of Analysis of hydrocarbons stability under thermobaric conditions … · 1 –sample spectra before...
Aleksandr Serovaiskii, A. Kolesnikov, V. KutcherovGubkin Russian State University of oil and gas, KTH Royal Institute of Technology e-mail: [email protected]
Biogenic petroleum origin theory Abiogenic petroleum origin theory
Analysis of hydrocarbons stability under thermobaric conditions of the Earth crust and the upper mantle
Formation of natural-gas-like hydrocarbons mixture from inorganicsubstances or from individual hydrocarbons under conditions of theupper mantle had restarted discussions on the problem of petroleumformation and hydrocarbons properties in general. While individualhydrocarbon compounds under pressure were studied already to acertain extent, raw natural petroleum had never been loaded indiamond anvil cell or big press but two published works devoted tothermal conductivity measurement.
The purpose of my research was to find main thermobaricregularities of petroleum behavior: temperatures and pressures ofvitrification, crystallization, possible chemical changes like cracking,
dissociation or condensation.Crude oil stability was investigated in the earth crust thermobaric
conditions (up to 450ºC and 1,5 GPa) and upper mantle thermobaricconditions (up to 1000ºC and 5,5 GPa). The result of the experimentsshowed that crude oil could save its stability in such conditions. Thecrude oil deposits can be situated much deeper in the earth crust thanthe organic oil and gas origin theory claims. Some possible reactions ofcrude oil and iron compounds in upper mantle conditions weremodeled and carried out (up to 2000+ºC, up to 10 GPa). Iron carbidesand hydrides were obtained. These substances may take part in deepcarbon and hydrogen cycle.
Abstract
Petroleum stability in the Earth crust
Fig.2. Object – Fischer-Tropsh synthetic oil (received from Dr. K.G. Ione (Zeosit Co.) chromatogram
toluols, xylolsalkanes to C9 arenes C11+
320 °C 0,7 GPa, 3 hours heating (20-30 km)
1 – sample spectra before heating2 – sample spectra after heating
420 °C 1,2 GPa, 3 hours heating (30-45 km) 450 °C 1,4 GPa, 12 hours heating (35-50 km)
Fig. 4. Experiments result
The theory of biogenic petroleum origin claims that there is a “crude oil window” – the range of depth in the Earth crust,where crude oil deposits may occur. It should be no oil deposits deeper than this “oil window” level, only gas deposits. In deeperconditions crude oil will be cracked. But such deep crude oil deposits were found. They are explored successfully in industrialpurposes.
So the main goal of the experiment was to check till what depth crude oil can keep its stability. The investigations were madein Diamond Anvil Cells (DAC). The main goal was to investigate the petroleum stability in TP conditions corresponding to the Earthcrust. Crude oil showed high luminescence in Raman spectroscopy (Fig.1), so it was impossible to see any picks on the spectra. Tosolve this problem the synthetic oil was taken as an experiment sample (Fig.2). It was a mixture of hydrocarbons with knowncomposition similar to gas condensate (very light oil).
To heat the sample the resistive heating was used. To control pressure and temperature Ruby and Sm:YAG were used[1,2],the thermocouple was used for additional temperature control (Fig.3). The temperature range was 320 - 450 °C, the pressurerange was 0,7 - 1,4 GPa (up to 50 km depth).
It was carried out three experiments to investigate the petroleum stability in the Earth crust TP conditions - P=0,7 GPa, T=320°C (20-30 km), 3 hours; P=1,2 GPa, T=420 °C (30-45 km), 3 hours; P=1,4 GPa, T=450 °C (35-50 km), 12 hours. The experimentalresult showed sample stability in such TP conditions (Fig.4). The Raman spectra of the sample after heating was the same as theRaman spectra before heating.
Diamond picks
HC picks
HC picks
Diamond picks
HC picks
HC picks
Diamond picks
HC picks
HC picks
Diamond picks
HC picks
HC picks
Diamond picksHC picks
HC picks
Diamond picks
HC picks
HC picks
Fig.1. Raman spectra of crude oil (Astrakhan deposit) at different pressures
Fig.3. DAC with resistive heater and thermocouple
In 1877 the Russian chemist Dmitry Mendeleev published a hypothesis that received a name of carbidetheory of petroleum formation: 1) there is iron in the Earth’s interior, 2) at least partially it is in the reducedstate and in the compounds with carbon, 3) water can reach metal (mostly iron) carbides and formpetroleum [3,4,5]. This hypothesis lost its power when petroleum composition was more thoroughlyinvestigated and compared with products of carbide-water reactions.
While formation of petroleum from carbides in Earth’s interiors and its migration upwards is arguable,important role of hydrocarbon fluids in subducting slabs became evident recently. Oceanic lithospheretogether with petroleum deposits located both in sediment layer and basement rocks is transferred into theEarth by subduction [6]. To get information about possible transformations of iron compounds in thesubducting slab petroleum-ferropericlase ((Mg,Fe)O) system was investigated in the range of thermobaricconditions corresponding with the depth up to 280 km.
The initial sample assemblage consisting of a thin foil of 99% 57Fe-enriched ferropericlase with 20 %57FeO and crude oil was loaded in DAC. Double-side heating with optical fiber-based lasers (50W and100W) was used to produce temperatures that were measured by means of multi-wavelengthspectroradiometry (Fig.1). Mossbauer’s spectroscopy was used for sample analysis.
Two series of experiment were held – at 6,9 GPa and 9,5 GPa. The first heating was at 1000°C(100)during 5 minutes. After the first heating the cell was cooled and the Mossbauer’s spectra was made. Afterthat the cell was heated the second time at 1500°C(100). Then the cell was cooled and the Mossbauer’sspectra was made. The results of the experiments are shown on the Fig.2. At 6,9 GPa and 1500°C ironhydride was generated, at 9,5 GPa and 1500°C iron hydride and iron carbide were generated [7,8].
If formation of carbides and hydrides is possible, then may be pressure will significantly change thecomposition of hydrocarbons mixtures producing from carbide-water interaction? Probably Mendeleev wasnot so wrong? Observation of carbides formation from natural petroleum and ferropericlase in mantlemodeling materials let us to suggest existence of these substances in real geological conditions. On thedepth of 200-210 km in the presence of FeO iron hydrides (FeH) is formed. In the deeper zone (depth of280-290 km) the mixture of iron hydride (FeH) and iron carbide-cohenite (Fe3C) could be observed.)
Our results identify novel mechanisms that can lead to one of the possible carbon cycle: hydrocarbons-iron hydrides and carbides formation-hydrocarbons.
Carbides and hydrides from petroleum. Mendeleev’s carbide theory reverse?
“The War” of Petroleum generation paradigms
Hydrocarbons are generated in upper mantle layer from donors of carbon andhydrogen in extreme thermobaric conditions. Deep fluid goes up through migrationchannels and formats crude oil and natural gas deposits in Earth crust.
Tiny sea plants and animals died and were buried on the ocean floor.Over time, they were covered by layers of sediment and rock. Overmillions of years, the remains were buried deeper and deeper. Theenormous heat and pressure turned them into oil and gas.
Fig.1. The laser heating unit with DAC
Fig.2. Results of the laser heating experiments
What theory is right in this dispute? How was petroleum generated on our planet and how did it occur in the Earth
crust?
Conclusions1. Petroleum can be stable at the Earth crust TP conditions up
to 50 km depth (450°C, 1,4 GPa, at least during theexperimental time). We can suggest that deep crude oildeposits may occur in the Earth crust (deeper than 10 km).
2. Iron carbide and iron hydride can be generated from crudeoil and FeO and exist at upper mantle TP conditions (up to280 km). Our results identify novel mechanisms that canlead to one of the possible carbon cycle: hydrocarbons-ironhydrides and carbides formation-hydrocarbons.
Future plans1. To find the thermobaric conditions limit of hydrocarbons stability.2. To investigate a new analysis method that can be applied for crude
oil sample.3. To investigate petroleum stability in the porous rock at thermobaric
conditions corresponding to the Earth crust and upper mantle.4. To make an experiment with iron carbide, iron hydride and water at
TP conditions corresponding to the Earth crust and upper mantle.5. To investigate the possible mechanisms of petroleum chemical
reactions at TP conditions corresponding to the Earth crust andupper mantle.
What is petroleum?"Petroleum is a complex mixture ofnaturally occurring hydrocarboncompounds found in rock.Petroleum can range from solid togas, but the term is generally usedto refer to liquid crude oil”(Schlumberger Oilfield Glossary)
Exploration Transportation Refining
1. D. Trots et al., High-temperature structural behaviors of anhydrous wadsleyite and forsterite, American Mineralogist, Volume 97, 2012, pages 1582–1590
2. H.K. Mao et al., Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions, Journal of geophysical research, vol.91, NO 5, 1986, p. 4673-4676
3. Zhurnal Russkogo Himicheskogo I Fizicheskogo Obschestva pri imperatorskom S.-Peterburgskomuniversitete, V.9, N.2, sec.1, 1877, p. 36-37
4. Mendeleev, D., L'Origine du pétrole. Revue Scientifique, 2e Ser., VIII, 1877, p. 409-4165. Set of D.I. Mendeleev works, Izdatelstvo Akademii Nauk SSR, Leningrad-Moscow, 1949, V.10, p. 228-244
6. D. A. Sverjensky at al., Important role for organic carbon in subduction-zone fluids in the deep carbon cycle, Nature Geoscience, published online: 17 November 2014, DOI: 10.1038/NGEO2291
7. O. Narygina et al., X-ray diffraction and Mössbauer spectroscopy study of fcc iron gydride FeH at high pressures and implications for the composition of the Earth's core, Earth and Planetary Science Letters, 307, 2011, p. 409–414
8. C. Prescher et al., Structurally hidden magnetic transitions in Fe3C at high pressures, Physical review, B 85, 140402(R), 2012
Literature
Before heating
After the first heating, 1000°C
After the secondheating, 1500°C
6,9 GPa 9,5 GPa
FeO
α-Fe (11%)
FeH (27%)FeH (34%)FeH (24%)
Fe3C (36%)FeO (28%)
FeO
FeO
FeO
FeO (40%)
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