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17ХИМИЧЕСКИЕ НАУКИ
PACS:: 621.436
EFFECT OF GAMMA iRRADiATiON ON GASOLiNES
L. JABBAROVA(DOS), N.IBADOV(DOS), I.MUSTAFAYEV(PROF), A. MIRZAYEVA
Institute of Radiation Problems, Azerbaijan National Academy of Sciences, 9 F. Agayeva str. Baku,
AZ1143, Azerbaijan.
Summary: The ability of fuel components to maintain their chemical composition in the conditions of operation under changes in temperature, radiation exposure, under the influence of metals has an important practical value. Under radiation exposure, the processes of destruction and polycondensation of hydrocarbon molecules can occur. In this case, the flow of processes depends on the temperature and the absorbed dose of the emission. Samples of AI-92 gasoline from Azerbaijani oil were used as a research object. Laboratory studies were performed on the gamma source Co60 at a dose of P = 0.076 Gy / s at room temperature at different absorbed doses of D = D = 27-78 kGy. The effect of ionizing radiation on the structural-group composition of gasoline in static conditions by the usual method before and after the study was studied.
Keywords: fuel, radiolysis, IR- spectrum, gas, gamma source, gasoline.
INTRODUCTION
Under the influence of radioactive radiation, the structuring of organic compounds and their decomposition occur simultaneously. Decomposition always continues because gas is released during the radiolysis of all organic compounds. Decomposition leads to a decrease in viscosity in liquids and an increase in softness in solids. Clarifying the effect of radiation on the overall composition of the fuel, the relationship between the requirements for the composition of a fuel and its radiation resistance is a very important task of research. As a result, the performance of the fuel deteriorates at ambient temperatures. To date, many works have been published on the effects of ionizing radiation on various hydrocarbons and liquid fuels [1-11], and these studies allow us to establish the general laws of radiolysis of organic compounds. When choosing fuels and lubricants for use in the conditions of exposure, some questions arise: do ordinary materials have adequate radiation resistance. Is it possible to increase their stability at the expense of insignificant changes in the composition by introducing special additives and what are the prospects for the synthesis of new materials, having satisfactory characteristics in the absence of abnormalities.When studying radiation exposure to materials, two types of experiments are possible: first, the study of exposure to radiation from other external factors and the definition of operational characteristics of the fuel and lubricants; secondly, accounting for emissions into the complex with other external factors. At an altitude of 2030 km of hydrocarbon fuel in aircraft can be observed under the influence of space particles of large energy. In connection with this, as well as in connection with the discovery of the possibility of developing new technological processes with the use of energy from radioactive emissions, it is necessary to study the impact of different types of oil and gas emissions. Determining the impact of the impact on the overall composition of hydrocarbon fuels is very important for any research, directed at the establishment of interrelationships with the requirements for the composition of the fuel and its radiation resistance. It is especially interesting to study the effects of exposure to aromas in fuels, as the radiation resistance of aromatic hydrocarbons is known, but they have an unfavorable effect on the thermal resistance of rocket fuel. The impact of radioactive emissions falls mainly on the ionization of the environment, absorbing energy, and on the induction of free radicals, depending on the concentration at which the radical-chain process will develop. Under these conditions, dimers and polymers such as products of recombination of radicals and ions are formed simultaneously with
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low-molecular compounds of fracture character in fuels. In the absence of oxygen, these processes are enhanced and acquire an oxidizing character. The effect of exposure to hydrocarbons depends on their chemical structure, the composition of the mixture and, in a significant measure, the admixture of other substances.The availability of unlimited hydrocarbons in fuel, as well as such lightly acidic compounds as mercaptans, determines the chemical stability of fuel during long-term storage. When storing such fuels, the content of resin is reduced in them, the content of mercaptans is reduced and sediments are formed. Significantly increases the speed of formation of tar in fuels solar light and radiation.Aromatic hydrocarbons are characterized by some specific features. By the ability to form under the action of polymer emissions they are attached to alkenes. However, aromatic hydrocarbons differ in their relatively high radiation resistance. It is noted that in the mixture with hydrocarbons of this structure they protect the latter from the action of radiation. All this attracted special attention to the study of radiolysis of aromatic hydrocarbons.
METHODOLOGY
The study was conducted with the use of gasoline with the addition of different percentages of benzene. The kinetics of the processes were studied at a temperature of T = 20 ° C, the power of the exposure dose P = 0.072 Gr / s, the absorbed dose D = 27-78 kGr, the concentration of benzene 1, 2, 4 and 6%. IR spectra of absorption of samples in the form of a film of thickness d = 1 are registered on the spectrometer Varian 640-IR (Varian) in the frequency range 4000—400 cm -1. The stripping is performed as in [12].
Chromatomasspectra were analyzed on AGT GC / MS Gerstel.
x106 +TIC SIM N1.D
Counts vs. Acquisition Time (min)
Benzene ug/l 0,171 47726654 39349877
Toluene ug/l 0,103 32513863 36751118
Ethylbenzene ug/l 0,030 9240766 11108771
m+p-Xylene ug/l 0,100 33402961 40033316
o-Xylene ug/l 0,025 15210809 18490651
Total BTEX ug/l 0,429 138095053 145733733
C6-C9 Aromatics ug/l 0,429 138095053 145733733
n-Hexane ug/l 0,000 4486305 6254213
n-Heptane ug/l 0,381 9189571 11652816
n-Octane ug/l 0,290 4655858 5920501
n-Nonane ug/l 0,239 2040759 2773995
C6-C9 Aliphatics ug/l 0,910 20372493 26601524
GRO (C6-C10) ug/l 5,810 234781216 269850176
GRO (C6-C10) mg/l 0,006 234781 269850
GRO (C6-C10) % 0,000 23,5 27,0
Halogenated VOCs ug/l 6,483 8157319 9693406
Chlorobenzenes ug/l 4,770 4579 3233
Benzene g/L 47,7 39,3
Toluene g/L 32,5 36,8
Ethylbenzene g/L 9,2 11,1
m+p-Xylene g/L 33,4 40,0
o-Xylene g/L 15,2 18,5
Total BTEX g/L 138,1 145,7
Benzene % 4,77 3,93
Toluene % 3,25 3,68
Ethylbenzene % 0,92 1,11
m+p-Xylene % 3,34 4,00
o-Xylene % 1,52 1,85
Total BTEX % 13,81 14,57
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
Wavenumber
Gasoline (clean)
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 4(
Waven umber
240 hours immediately after radiation (2%)
240 hours 2% after 1 month of radiation
Gasoline (clean)
700-600 cm-1-alkynes and triple bonds.
770-730 cm-1 non-flat deformations of the SN in the area of 1000-650 cm-1, monolayers
1385-1370, 1470-1435 oscillations of ligaments -CH3 in alkanes
1600-1575 cm-1oscillations of an aromatic ring
2940-2915 cm-1oscillations of bonds -CH2- in alkanes
3070-3020 cm-1-heterocyclic compounds of pyridine and quinolin
240 hours immediately after radiation (2%)
615-690 cm-1 Nitrites RO-N = O
1385-1370, 1470-1435 cm-1 oscillations of ligaments -CH3 in alkanes 2940-2915 cm-1oscillations of bonds -CH2- in alkanes 3670-3580 cm-1valence oscillations O-N, free groups O-N
240 hours 2% after 1 month of radiation
720-740 cm-1 oscillations of the ligaments (CH 2) x in alkanes
1470-1435,2885-2860, 2975-2950 cm-1 swaying ties -CH3 in alkanes 2940-2915 cm-loscillations of bonds -CH2- in alkanes.
DISCUSSION
Immediately after irradiation, the groups (CH2 2927 cm-1) decrease by a factor of 6. The number of aromatic groups is also reduced (1607 cm-1) 4 times. A month after irradiation, these groups increase, which is explained by the polymerization process.
Under the influence of ionizing radiation, the destruction of gasoline molecules occurs. As a result of the action of accelerated electrons, ions, electrons, and excited molecules are formed. The interaction of these particles leads to the formation of radicals, which, as a result of recombination by the chain mechanism, form radiolysis products [11].
As a result of radiolysis at the temperature of the surrounding air, the operating properties of petroleum fuels and oil are deteriorating; such deterioration is not a significant table, but it acquires a serious value, if from the heat and the problem requires high thermal stability. Under such conditions, a particularly negative role will be played by organic non-hydrocarbon additives, mineral additives (soil dust, corrosion products and metal wear), additives containing metals, phosphorus, elements and others. At elevated temperatures, the negative effect of heating fumes and masels, which occur in contact with oxygen in the air, is more pronounced than its absence. It is possible to assume that the farther we will be able to select such a composition of petroleum fuels and oil, which at higher temperatures will be better to counteract the action of radioactive exposure. This, apparently, will be achieved not only by changing the hydrocarbon composition of petroleum products, but also by introducing additives. The amount of decomposed hydrocarbon increases with increasing irradiation intensity and total irradiation dose. As a result, at ambient temperature, the performance properties of gasoline deteriorate. During storage of such fuels, the content of actual resins in them increases, the content of mercaptans decreases and a precipitate forms. By changing the hydrocarbon composition of oil products due to composition changes or the introduction of additives, it is possible to select a fuel composition that will better withstand the effects of radioactive exposure.
Conclusion: The rate of polymerization during the radiolysis of a mixture of gasoline benzene depends on the concentration in the system and the absorbed dose.
REFERENCES
1. Jabbarova L.Y., Mustafayev I.I.Radiolysis of Diesel Fuel. High Energy Chemistry,2021, v.55, p. 37-39.
2. Jabbarova L.Y., Mustafaev II..Radiation effects of organic fuels. Radiochemistry, 2021, Vol.63.№3 p.296-300.
3.L. Y. ^^a66apoBa, H. H. Mustafayev. Study of radiolysis of diesel fuel. Chemistry of high energy 2021, v. 55, № 1, p. 39-41.
4. Jabbarova L.Yu., Mustafaev II. High temperature radiolysis of diesel fuel. J. Application. Spectroscopy, T. 85, No.4, 2018, C. 634-638.
5. Jabbarova L.Y., Mustafayev II II The study of the effect of ionizing radiation on some properties of diesel fuel. J. Energy, Environment and Chemical Engineering. USA, -V. 2, Issue 4, -2017, p. 4145.
6. Jabbarova L.Yu., Mustafaev II, Melikova S.Z. The effect of radiation on petroleum fuels. "International Journal of Applied and Fundamental Studies", "Academy of Natural Sciences" Research Center, Moscow, № 7 (part 2) .2017, p. 239-243.
7. Jabbarova L.Yu, Mustafayev II, The Impact of Radiation on the Technical and Operational Quality of Gasoline .Journal of Energy, Environment and Chemical Engineering. USA. 2017, Volume 2, v.4 p. 62-66.
8. Denisov A.V., Dubrovsky V.B., Soloviev V.N. Radiation resistance of mineral and polymer building materials. M . Ed. MEI, 2012, 384 p.
9. Ponomarev A.V., Holodkova E.M., Ershov B.G. Electron-beam synthesis of fuel in the gas phase.Radiation Physics and Chemistry. 2012, V. 81, Is.9, p. 1440-1444.
10. Ponomarev AV, Tsivadze A.Yu. Liquidation of gaseous alkanes under electron radiation. Reports of the Academy of Sciences, 2006, Volume: 411, No 5, p. 652-658.
11. Milinchuk VK, Klinshpont ER, Tupikov VI Fundamentals of radiation resistance of organic materials. M .: Energoatomizdat, 1994. 256 p.
12. K. Nakanishi. Infrared spectra and structure of organic compounds. Moscow, Mir. 1985. PACS:: 621.436
POST-RADIATION PROCESSES IN OLEFINITE LIQUID SYSTEMS
L. JABBAROVA, I. MUSTAFAYEV, R. AKBAROV
Institute of Radiation Problems, Azerbaijan National Academy of Sciences, 9 F. Agayeva str. Baku,
AZ1143, Azerbaijan.
Abstract: The main reason for the low stability in hydrocarbon fuels is the presence of olefin compounds. Alkenes are very reactive, they enter into bonds at the sites of double and triple bonds, polymerization reactions are characteristic. The study of the radiolysis of mixtures of saturated and unsaturated hydrocarbons at various concentrations makes it possible to draw conclusions about the nature of the main radiation-chemical processes. In fuels containing a large amount of unsaturated hydrocarbons, coking capacity increases and color deteriorates during irradiation. Structuring is physically manifested in organic liquids in a change in viscosity and density. The amount of decomposed hydrocarbon increases with an increase in the total radiation dose. Changes occurring at the time of irradiation may be reversible or irreversible. Reversible effects depend on the dose rate. Irreversible changes in the properties of organic fuels depend on the absorbed dose, temperature and persist after irradiation, causing chemical transformations of molecules. The studies were performed using radiolysis of a model hydrocarbon mixture, the hexane / hexene system. Changes in the iodine number and molecular structure of liquid fuels, as well as the kinetics of gas formation were studied as indicators of the processes. The dependence of the speed of the post-polymerization process on the concentration and dose of olefin was studied.
Keywords: olefin, iodine number, post-polymerization, liquid fuel.
INTRODUCTION
Under the influence of radioactive radiation, the structuring of organic compounds and their decomposition occur simultaneously. Decomposition always continues because gas is released during the radiolysis of all organic compounds. Decomposition leads to a decrease in viscosity in liquids and an increase in softness in solids. Clarifying the effect of radiation on the overall composition of the fuel, the relationship between the requirements for the composition of a fuel and its radiation resistance is a very important task of research. As a result, the performance of the fuel deteriorates at ambient temperatures. To date, many works have been published on the effects of ionizing radiation on various hydrocarbons and liquid fuels [1-11], and these studies allow us to establish the general laws of radiolysis of organic compounds.
METHODOLOGY
The studies were performed using radiolysis of hexane / hexene mixture. The kinetics of the processes were studied at temperature T=20oC, radiation dose rate P=0.072 Gy/s, absorbed dose D = 27-78 kGy, olefins at concentrations of 5, 10, 20 and 40%. Iodine number was determined in
