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0УДК 621.436 , 665.734
STUDYING THE RADIATION RESISTANCE OF SYNTHETIC OILS OBTAINED
FROM PETROLEUM BITUMEN ROCKS
L.YU JABBAROVA *., Z. SH. ZAKHAROV
Institute of Radiation Problems of the Ministry of Science and Education of Azerbaijan
I.I .MUSTAFAEV
Azerbaijan University of Architecture and Construction AZ 1143, Baku, st. F. Agayev 9
Abstract. The results of studies of radiation effects on artificial oil from oil-bituminous rocks of the Azerbaijan field are presented. Petroleum bituminous rock is a natural material formed from oil in the upper layers of the earth's crust as a result of the evaporation of light fractions from it, the natural deasphalting of oil and the processes of interaction of its components with oxygen. The studies revealed the formation of gases and changes in the properties of liquid residues during the processing of artificial oil obtained in laboratory conditions, and also studied the radiation resistance of various fractions of oil from bituminous rock. The studies were carried out under the influence of y-radiation Co60 MRKH-y-30 in a wide range of absorbed doses (43-216 kGy) in air and vacuum. at dose rate P=0.5 Gy/s. The results of chromatographic, chromatospectroscopic and IR spectroscopic studies of artificial oil samples are presented. The results of such studies make it possible to evaluate the possibility of obtaining petroleum products for various purposes using the radiation-thermal method from oil-bituminous rock, as well as the use of these materials to isolate radioactive sources from the environment.
Key words: oil bituminous rock, artificial oil, gamma radiation, IR spectrum, radiation chemical yield, optical density, chromatography, chromatospectrum
Introduction
Today, the production and processing of heavy oil and natural oil-bituminous rocks account for less than 1% of their reserves, which amount to more than 810 billion tons. Oil-bituminous rocks are oxidized, highly viscous, dense oils of semi-liquid and solid consistency with a high content of sulfur, oils, resins and asphaltenes and have a high content of vanadium, nickel, and molybdenum [1 p. 54-55.,2 p. 34-37, 3.p.148-155,4 p.1-6.,5p. 58-66.]. They are substitutes for oil. They can be used as raw materials for road construction, waterproofing, anti-corrosion work, and for the production of varnishes and paints. High-viscosity oils and bituminous rocks can be used to produce marketable bitumen, which makes their extraction economically feasible. Studies of the effects of ionizing radiation on petroleum fuels and hydrocarbon mixtures make it possible to establish the patterns of gamma radiolysis of organic materials [6p.584-592,7.p 418-425,8.p. 373-377.,9. p. p.216-226., 10 p. 1-6.]. In England, Venezuela, Mexico, and Italy, work is underway to extract vanadium and molybdenum from oil-bituminous rocks [11p. 27- 31.,12p. . 1509-1529.]. Many physicochemical properties of hydrocarbon raw materials, including calorific value, depend on the H/C ratio (Table 1). Table No. 1. H/C ratio in organic fuels
№ organic matter H/C Q, MJ/kg
1 Natural gas 4 55
2 Normal hydrocarbons >2 45-50
3 Light petroleum products 1,8-1,9 46
4 Heavy oil fractions 1,3-1,5 42
5 Coals <1 29
6 Organic part of petroleum bituminous rock 1,6 29
The purpose of the work is to study the method of radiation-thermal processing of oil-bituminous rocks, the possibility of using this technology to obtain artificial oil, as well as to study the radiation resistance of refined products.
Research methods
Artificial oil from bituminous rocks was produced by burning in a Retort Heating Jacket at a temperature of 950F (510C). From 375 g of rock, 50 ml of artificial oil was obtained. Rock composition (in%): oil - 22, water - 6, sand - 72. Oil samples weighing 2 g were placed in 30 ml molybdenum glass ampoules and the air was sucked out to a pressure of 0.1 mm Hg. Art. The ampoule was separated from the apparatus by welding and irradiated at different times in the MPX-y-30 (Co60) radiation installation under vacuum and air conditions. The dose rate of the radiation source was P=0.49 Gy/s, the absorbed dose in the intervals D=34.5-172.8 kGy. For chromatographic analysis, artificial oil samples were dried with anhydrous sodium sulfate (Na2SO4), diluted with dichloromethane (CH2Cl2) and chromatograms were recorded on a GCMS Trace DSQ chromatography-spectrometric apparatus (Thermo Electron, Finngan USA, 2005) in the mass range from 35 to 400 m/z ( m/z is the ratio of ion mass to charge). Based on the spectra of the identified components of the oil samples, chromatograms were constructed in the mass range and based on the spectra. Sample numbers: 12169 - original artificial oil; 12170 - 96 hours of irradiated artificial oil in air; 12171 - 96 hours of irradiated artificial oil in a vacuum. IR spectra of the samples were recorded on an M-80 spectrophotometer in the wavenumber range 700-4000 cm-1. The bands of the obtained spectra were assigned as described in [13 p.277.]. Gas products were analyzed by gas chromatography. Using IR spectroscopy, changes in the molecular structure of liquid products obtained from oil-bitumen rocks under artificial conditions under the influence of radiation were observed.
Experimental results
Figure 1 shows chromatograms of oil samples from natural bituminous rocks. The components in the original and irradiated samples of artificial oil were determined from the chromatograms.
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Fig. 1.
1 1 1 1—| 1 1 1—1 | 1 1 1—1 | 1 1—1 1 | 1 1—1 1 | 1—1 1 1 |—1 1 1 1 |—1 1 1 1—| 1 1 1 1—| 1 1 1—1 | 1 1 1—rr I 5 10 15 20 25 30 35 40 45 50 55
Time (min)
Chromatograms of the original (a) and irradiated artificial oil in air (b) and vacuum (c). The identified components of the original artificial oil are presented in Table No. 2
Table No. 2. Identified components of the original synthetic oil samples from natural
bituminous rocks
№ Component se time min Identified components of the original synthetic oil samples from natural bituminous rocks formula
1 4,17 Toluene С7Н8
2 7,37 p-Xylene C8H10
3 7,79 cis-2-Nonene C9H18
4 8,02 Nonane C9H20
5 9 Octane, 2,6-dimethyl- C10H22
6 9,65 1-Octyn-3-ol, 4-ethyl- C10H18O
7 10,09 Benzene, 1-ethyl-3-methyl- C9H12
8 10,56 Benzene, (1-methylethyl)- C9H12
9 10,74 1-Decene C10H20
10 10,92 Decane C10H22
11 11,31 1-Octanol, 2-methyl- C9H20O
12 11,75 Benzene, 1-ethyl-4-methyl- C9H12
13 13,3 1-Undecanol C11H24O
14 13,46 Undecane C11H24
15 14,67 Undecane, 6-methyl- C12H26
16 14,93 Benzene, 1,2,4,5-tetramethyl- C10H14
17 15,58 Cyclopropane, nonyl- C12H24
18 15,73 Dodecane C12H26
19 15,97 Undecane, 2,6-dimethyl- C13H28
20 17,67 1-Tridecene C13H26
21 17,8 Tridecane C13H28
22 18,81 1-Pentadecanol C15H32O
23 18,92 Cyclohexanol, 5-methyl-2-(1-methylethyl), [1R-(1à,2â,5à)l- C10H20O
24 19,64 1-Tetradecene C14H28
25 19,75 Tetradecane C14H30
26 20,73 Naphthalene, 2,7-dimethyl- C12H12
27 20,81 Tetradecane, 2,6,10-trimethyl- C17H36
28 21,45 2,6-Dodecadien-1-ol, 3,7,11-trimethyl,(E,E)- C15H28O
29 21,58 Pentadecane C15H32
30 21,92 1H-Indene, 2,3,3a,4,7,7a-hexahydro-2,2,4,4,7,7-hexamethyl C15H26
31 22,64 Naphthalene, 1,6,7-trimethyl- C13H14
32 23,19 1-Hexadecanol C16H34O
33 23,29 Hexadecane C16H34
34 24,84 1-Heptadecanol C17H36O
35 24,92 Heptadecane C17H36
36 26,4 8-Heptadecene C17H34
37 26,47 Octadecane C18H38
38 27,95 Nonadecane C19H40
39 29,37 Eicosane C20H42
40 30,49 Octadecane, 3-methyl- C19H40
41 30,72 Heneicosane C21H44
42 32,74 Allopregnane C21H36
43 33,26 Octadecane, 3-ethyl-5-(2-ethylbutyl)- C26H54
The components in the original and irradiated samples of artificial oil were determined from the chromatograms. Before irradiation, lighter hydrocarbons predominated - undecane, dodecane, tridecane, tetrodecane. hexadecane. After irradiation, eicosane, allopregnan, and octadecane are observed, which is associated with the occurrence of polycondensation and rearrangement processes in the molecular structure of artificial oil.
This oil is characterized by a high content of cyclic structures, especially aromatic compounds, which are concentrated in middle distillates. This explains its low hydrogen content and high density in the absence of heavy residual fractions.
Fig. 2 IR-spectrum of the initial sample of artificial oil obtained from bituminous rock
Fig.3. IR -spectrum of a sample of synthetic oil obtained from bituminous rock in irradiated
air during 48 hours
Fig 4. IR -spectrum of a sample of synthetic oil obtained from bituminous rock irradiated in
air for 72 hours.
Fig. 5. IR spectrum of a sample of artificial oil from bituminous rock irradiated under
vacuum conditions for 72 hours.
Fig. 6. IR spectrum of a sample of artificial oil from bituminous rock irradiated in air for 120
hours
Fig.7. IR-spectrum of a sample of artificial oil from bituminous rock irradiated under vacuum
during 120 hours
The effect of gamma radiation on the structural and group composition of synthetic bituminous oil samples was studied. In the IR spectrum of the original artificial oil, absorption bands were observed at 740 cm-1, responsible for the pendulum vibrations of the -CH2 group, and bands of bending vibrations at 1380 cm-1 and stretching vibrations at 2860, 2960 cm-1, characteristic of the methyl groups of CH3. The spectrum contains vibrations characteristic, respectively, of the =CH2 and C=C-bond groups of unsaturated hydrocarbons, corresponding to non-planar bending vibrations
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of the substituted benzene ring. The absorption band at 1720 cm-1 corresponds to the carbonyl group C=O. Absorption bands are observed in the region of 1020-1160 cm-1 with maxima at 1025, 1070, 1120, 1160 cm-1, corresponding to oxygen-containing groups (C-O-, C-O-O, O-H). Due to the long-term presence in the environment, there are high contents of oxygen-containing compounds in the composition of oil-bituminous rock. The presence of these reactive groups determines the higher adhesion force of the binder components to the rock (adhesive properties) compared to artificial compositions based on petroleum products. But when irradiated they easily split. The content of oxygen-containing groups decreases during irradiation due to their transition to heavy fractions. IR spectra of the samples (irradiated in air for 72 and 120 hours, respectively) with the IR spectrum of the original product, it can be concluded that the intensity of the absorption bands responsible for paraffin, unsaturated, aromatic hydrocarbons, as well as oxygen-containing compounds, significantly decreases in the following sequence: intensity of absorption bands of the original oil > irradiated oil in air 72 hours > irradiated oil in air 120 hours. With an increase in the absorbed dose, the optical densities of the absorption bands of functional groups in the samples also decrease.
THE DISCUSSION OF THE RESULTS
Energy production and consumption are the basis for economic development and social progress, climate change on Earth, therefore low-carbon energy issues play a decisive role in the field of sustainable development. The use of electron beam processing of solid fuels and high-viscosity oils results in significant energy savings. This will have a positive effect in terms of environmental protection. When producing electricity, materials are used that are environmental pollutants. The use of coal in thermal power plants leads to the appearance of acid rain due to the formation of nitrogen and sulfur oxides during its combustion and their subsequent release into the atmosphere with exhaust gases. An economy that is based on low-carbon energy sources has minimal emissions of greenhouse gases into the atmosphere, in particular carbon dioxide.
Exposure to radiation is essentially an initiation reaction that produces free radicals. Temperature ensures the removal of the activation barrier to chain continuation reactions. In the absence of temperature, changing the dose rate does not affect the radiation-chemical yield. With the simultaneous influence of thermal and radiation factors, under conditions of purely thermal reactions, temperature is more influential than radiation power. The radiation resistance of functional groups, especially oxygen-containing and olefinic groups, depends on the potential of the excited state and ionization, which determines the processes of energy transfer between components. In the presence of polyaromatic structures, the absorbed energy is dissipated by n electrons and bonds in functional groups are broken. Irradiation of these samples in air increases the destruction process, but the yield of products is relatively small. To increase the radiation-chemical yield of gases and obtain a chain mechanism for the decomposition of hydrocarbons in such systems, it is necessary to use high temperatures. At high temperatures, the process of decomposition of the starting material occurs effectively due to termination reactions in the presence of radiolytic hydrocarbon radicals. To prevent recombination processes of chain breaking under the combined influence of heat and radiation, it is necessary to select such values of temperature and dose rate so that the radiation effects are maximum [14 P.278.].
CONCLUSIONS
1. It is possible to use bitumen oil as a feedstock for the production of waterproofing material, which can be used in conditions of radiation exposure, in nuclear energy and for the disposal of radioactive waste.
2. Based on IR spectra, the mechanism of destruction effects occurring in liquid products is discussed.
3. To produce hydrogen, hydrocarbon gases and olefinic hydrocarbons from artificial bitumen oil, the combined effect of ionizing radiation and temperature is necessary, with a consistent value of temperature and radiation power.
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