International Journal of Petroleum and Geoscience Engineering Volume 04, Issue 02, Pages 66- ISSN: 2289-4713 Improved Measurement Method of Physical and Chemical Properties of Oil Products by Fewer Tests V. H. Nurullayev a, * a Technical Sciences State Oil Company of the Azerbaijan Republic (SOCAR), Republic of Azerbaijan. * Corresponding author. E-mail address: Veliehet1973@mail.ru A b s t r a c t Keywords: Distillation fractions, Flash point, Oil properties, Rheology, Kinematic viscosity. Recently the steady tendency to magnify of haul bulks, oil and oil products was outlined. Thus, in order to solve the problem on magnification of bulk of oil pumping and oil products, developments new or optimization of applied technologies of haul of oil and oil products taking into account their rheological behavior and operating characteristics of pipe-lines are indispensable. The main investigated parameters of various oil products are: boiling temperature, flash temperature, density, kinematic viscosity. It is shown, that at the additive in avia kerosene ТS-1 of gasoline А-76 in quantities to 5 % does not worsen quality of avia kerosene, and in quantity to 3 % - it is not reflected at all in its quality. Accepted: 15 Jun 2016 Academic Research Online Publisher. All rights reserved. 1. Introduction The statistical techniques employed are multivariate they consider the relationships between groups of tests and the two main statistical procedures used are principal components analysis and multiple regression analysis. A typical end product of this statistical approach has been the conclusion that the aromatics content; luminometer number and smoke point can be calculated from the gravity and aniline point of aviation kerosene fuels. The statistical techniques employed are described by US, Russian and Azerbaijan scientific groups [1, 2]. Control of gasoline quality. The tests on motor gasoline are in two groups, those relating to bulk properties and those concerned with trace properties. The only additives to influence bulk properties are the lead alkyls; the other additives are associated with trace properties. The bulk- properties tests on motor gasolines will then comprise some or all of the following: gravity, distillation test, Reid vapor pressure, a vapor/liquid ratio measurement, olefins content, lead alkyls content, research octane number, motor octane number, a distillate octane number. Trace-properties tests will include: 66 P a g e
Total sulfur, mercaptan sulfur, gums, anti-icing additives, detergent additives, ignition control additives, and inhibitors. These trace properties are effectively controlled by the additive addition and the refining route. For example, the sulfur and mercaptan sulfur contents will depend on the blend composition of the gasoline. A gasoline manufactured from, reformate and butanes will necessarily have such low sulfur and gum contents that testing of the blended gasoline for these will not be necessary. But a gasoline containing large amounts of heavy catalytically cracked material might need to be tested for these trace properties. The components used have known qualities and quantities employed are designed to meet the target quality of the blended gasoline. It is at this point that specification testing is carried out and relationships between tests can be exploited. Some of the most expensive items in the specification testing are the research octane ratings. It is worth trying to economize here. It is also worth using the information provided by the distillation test for control of front-end volatility. By examining the various relationships it was concluded that the following key qualities are generally justified: specific gravity, distillation parameters, and research octane number. This experimental information is supplemented by the blended lead alkyls content and the olefins content, which is calculated from the, olefins contents and quantities of the cracked components in the blend. The motor octane number and a distillate octane number are calculated, using linear equations, from the key tests. For example, the equation used to calculate the motor octane is: MON= 22,5 + 0,83 RON - SG - 20 SG - 0,12 olefins + 0,5 TML + 0,2 TEL (SG 60/60 0F., olefin percent volume, TNL and TEL in ml/ig) Because it is the most precise and widely used the research octane number was chosen as the key octane test. The precision of the research rating in many laboratories is twice as good as that of the motor octane rating. Some specification includes three clauses, using three different tests, to control the front-end volatility is within the specified limits. Consider the distillation Reid vapor pressure, and vapor/liquid ratio tests. The Reid vapor pressure can be calculated from distillation test data, and in most laboratories it is possible to calculate the Reid vapor pressure to within 1 psi. A calculated Reid vapor pressure result may then be used to replace the experimental result on gasolines that are not near the specification limit. 2. Theory It is obviously not economy to eliminate the vaporpressure test when manufacturing gasoline to the maximum vapor pressure. The correct procedure is to use the calculated vapor pressure to check the experimental result. Vapor/liquid volatility parameters may then be calculated from the vapor pressure and the distillation data. Use of equation to obtain certain specification points obviously has a limited future. The real 67 P a g e
lesson to be learned from the work is that critical specification tests have been identified, and that it is possible to construct specification that is much more efficient using only these key tests. For example, road antiknock control parameters should be based should be based on the research octane rating supplemented by properties that can be closely controlled, such as the lead alkyls and olefins contents. It is inefficient and quite unnecessary to have more than one experimental CFR rating on road antiknock control. Road antiknock quality is of course the most controversial and economically important control point in motor gasolines [3, 4]. The results of this work on gasolines have been successfully applied for motor-fuel quality control in BP and SOCAR refineries. Experimental vapor/liquid ratio measurements have been completely replaced by calculated results [5, 6]. The motor octane number test has been eliminated in most refineries and calculated values for distillate octane numbers are used extensively [7, 8]. Turbine-fuel quality. It is possible to consider the tests called for in Jet A and A-1 specifications in a similar way to that used with motor gasolines.in the group of tests associated with bulk properties, five are associated with the combustion or aromaticity of kerosines. These five tests are; gravity, aniline point, smoke point, luminometer number and aromatics content. Statistical analysis showed that these five were measuring only two independent properties. The two most informative tests were found to be gravity and aniline point. These were therefore selected as the key tests and equations were derived which enabled results of the other three tests to be calculated from the gravity and aniline point. The original work was carried out using data on 300 kerosines which covered wide ranges of gravities and aniline points. Subsequently, some data became available on the hydrogen content of jet fuels and it proved possible to calculate this property as well, from the gravity and aniline point [9, 10]. It is relatively easy to establish relationships between tests but more difficult to have the results accepted by the petroleum industry. To encourage use of calculated results, tables were constructed which listed the possible aniline points in 0F, and 0C., for particular values of the gravity in the Jet A and A-1 range, together with the corresponding calculated results of the smoke point, luminometer number, and aromatics content. These tables were circulated within the BP, SOCAR group and all the refinery and technical service laboratories. The results have been rewarding. In many instances the differences in standard between the experimental and calculated results are lower than the published estimates for the testing error standard deviation. This proves that many laboratories can calculate test results with a precision that is better than the quoted precision of experimental result. These tables were widely distributed by the Institute of Petroleum to member companies and to 68 P a g e
the ASTM (American), BNP (France), GOST (Russian) and DGMK (Germany). An IP subcommittee, concerned with improving test methods is presently considering the results of the work. Improvements in test methods and specifications are needed and should be carried out on an international basis. ASTM policy towards rationalizing testing will have major influence on the work. New test procedures. The increasing commitment to the petroleum industry to petrochemical industry to petrochemical production and the rapid development of gas-liquid chromatography (GLC) as an analytical technique have already influenced the activities of most petroleum laboratories. GLC is outstanding for compositional analysis of petroleum gasses and distillates. In the future it will be one of the most frequently used tests. At present GLC is being used mainly for individual hydrocarbon analyses. But there is a wide scope to use GLC to predict bulk compositional properties such as octane ratings, lash points, and viscosities. For example, GLC is the procedure invariably used for analysis of liquid petroleum gasses. It is then a simple matter to calculate bulk properties such as specific gravity and vapor pressure. However, it is not possible to get complete chemical analysis of motor gasolines or even motor-gasoline-blending components. But neither is it necessary to have a complete component analysis in order to calculate reformates by considering four individual hydrocarbons. GLC is capable of examining all distillate petroleum products including vacuum distillates. There is no technical reason why properties of petroleum distillates. There is no technical reason why properties of petroleum distillates should not be calculated from the GLC analytical data. The essential point is to use GLC analysis for the required amount of detail but not to try to get too detailed information. It is useful to calculate bulk properties from GLC data but the real value of this analysis is the fundamental chemical information it provides. This is more valuable in it is own right than when degraded to octane ratings or viscosities. For example, a research octane rating calculated from GLC is of no more use than a CFR research octane rating for predicting the performance of a gasoline under specified road-test conditions. But when supplemented by information such as the normal pentane plus normal hexane content (the two poor antic nock quality hydrocarbons in the front end of motor gasolines), a much better description of the low-speed antiknock quality of the gasoline is obtained. Similarly, the characterization of catalytic-cracker feedstocks can be achieved in several ways. One of the most important properties, however, is the n-paraffins. GLC provides this information directly but frequently it is degraded to the less meaningful distillation data. Of the existing bulk-properties tests it was obvious that some have a limited future while others are permanent. The specific gravity is of prime importance for quantity control but the value of this test has been 69 P a g e
underestimated for quality control. This test will be even more important in the future. The viscosity test is not important on light and middle distillates and could be eliminated but is important on lubricating and residual fuel oils. On light distillates the distillation, vapor pressure, and vapor-liquid ratio tests could already be replaced by GLC analysis. The various flash-point tests have outlived their usefulness. The hydrocarbon composition, specified by carbon number, is potentially a better guide to any of the properties which a flash-point test is intended to control. Instead of specifying that the flash point of Jet A and A-1 fuels should be greater than 110, it could be specified that jet kerosene should contain, not more than 1,5 % of hydrocarbons more volatile than normal octane, and that C4 and C5 hydrocarbons must not be present. The use of GLC analyses of crude oils for control of crude-oil distillation units and analysis of lightdistillate feedstocks is likely to increase rapidly. GLC is also attractive for analysis of crude-oil distillation units, side streams. Besides calculating the distillation parameters and flash points that have been traditionally used, it is most important for assessing fractionation and stripping. Exploiting GLC analysis at the present really rests on the fact that GLC is going to be widely used in the future anyway. It is to the petroleum industries advantage to make the most efficient use of the procedure. 3. Experimental Study Therefore according to the existing technological conditions all mix of such fuels is withdrawn from circulation or transferred to other oil product that leads to essential losses. The oil product used as a dividing stopper is received in the course of distillation of one of the contacting oil products in the range of temperatures of a boiling of hydrocarbons, the general for both of them. So, for example, if it is about consecutive pumping of the TC-1 aviation fuel which is boiling away in the range of temperatures from 150 to 250 0C between consignments of the A-76 gasoline which is boiling away in the range of temperatures from 35 to 195 0C a buffer product the rest after distillation of A- 76 gasoline at a temperature not below 150 of 0C is. If it is about consecutive pumping of the TC-1 aviation fuel which is boiling away in the range of temperatures from 150 to 250 0C between consignments of the diesel L-45 fuel which is boiling away in the range of temperatures from 190 to 360 0C. Buffer product is the distillate of diesel L-45 fuel condensed in the receiver refrigerator after distillation of diesel fuel at a temperature not over 250 of 0C. In other words, every time buffer oil product for a dividing stopper is formed by hydrocarbons, the general for this couple of pumped-over liquids. We conducted researches of the physical and chemical analysis of the oil products received from the Azerbaijani oil, TC-1 in accordance with GOST 10227-86 and A-76 gasoline in accordance with GOST 2084-77. Results of pilot studies are shown in table 1. The main indicators of various mixes of TC-1 and A-76 oil products were investigated: boiling temperature in accordance with GOST 2177-99; flash temperature in the closed crucible in accordance with GOST 6356-75; density in accordance with GOST 3900-85; kinematic viscosity in accordance with GOST 33-2000; acidity, mg the KOH on 100 70 P a g e
sm3 of fuel in accordance with GOST 5985-79; concentration of the actual pitches, mg on 100 sm3 of fuel in accordance with GOST 1567-97; test on a copper plate at 100 0C on GOST6321-92; temperature of the beginning of crystallization 0C in accordance with GOST 5066-11; mass share of the general sulfur, % in accordance with GOST 19121-73; mass share of mercaptans sulfur, % in accordance with GOST 5066-11; mass share of hydrogen sulfide, % in accordance with GOST 17323-71; vapors pressure, kpa (mm of mercury.) in accordance with GOST 1756-2000; watersoluble acids and alkalis in accordance with GOST 6307; Mas. share of aromatic hydrocarbons, % in accordance with GOST 6994-74; height of a smoke point flame, mm. in accordance with GOST 4338-91. fuel, in quantity to 3% - at all isn't reflected in its quality. The technological scheme of consecutive pumping of oil products with the dividing, buffer stopper consisting of hydrocarbons, the general for this couple of transported liquids doesn't demand changes in established practices and doesn't provide use of the special equipment. 4. Results and Discussion Results of pilot studies of physical and chemical properties of various mixes of TC-1 and A-76 oil products are shown in table 2. All results lie within accuracy and repeatability of laboratory analyses. Schedules of dependence of change of density, viscosity and fractional composition of mixes of TC-1 and A-76 oil products from a mass fraction of gasoline which are submitted in fig. 1-3 respectively are constructed. Apparently from these drawings calculations for the considered mixes by rules of additively well describe results of measurements only for viscosity parameter. In other cases deviations of the measured sizes from the settlement are observed. According to the reasons, such deviation in particular violations of structures of the studied systems [11]. Researches also showed that at an additive in TC-1 aviation fuel of A-76 gasoline in quantities to 5% doesn't worsen quality of aviation 71 P a g e
A-76 TC-1 Carrying out Characteristic Standard Actual Standard Actual methods analysis Boiling the initial 35 37 150 148 GOST temperatur, 2177-99 0 С I distit 10%. 70 67 165 161 I distit 50%. 115 109 195 183 I distit 90%. 180 172 230 223 Flash point in the closed cup 0 C - - 28 35 GOST 6356-75 Density 20 0 C, kg/m 3 Is not normal 754,2 775,0 789,6 GOST 3900-85 Kinematic viscosity, 20 0 C, cst Is not normal 0,5432 1,25 1,51 GOST 33-2000 Acidity, mg the KOH on 100 cm 3 of fuel 100 cm 3 of fuel Is not normal Concentration exs. gum, mg on 100 cm 3 of fuel 5 0,9856 0,7 0,42 GOST 5985-79 0,2351 5 0,3843 GOST 1567-97 Test on a copper corros. at 100 0 C stable stable stable stable GOST 6321-92 The flash temperature determined in the closed crucible, 0 C - Temperature of the beginning of crystallization 0 C - Mass share of the general sulfur, % 0,10-28 34 GOST 6356-75 - -60-68 GOST 5066-11 0,032 0,25 0,068 GOST 19121-73 Mass share of merkaptan. sulfur, % - - 0,005 0,002 GOST 5066-11 Mass share of hydrogen sulfide, % - - Absence Absence GOST 17323-71 Reid vapour pressure, Kpa (mm of mercury.) 66,7 (500) 43,6 (327,04) - - GOST 1756-2000 Water-soluble acids and alkalis Absence Absence Absence Absence GOST 6307 Masses. Share of aromatic hydrocarbons. % - - 22 16 GOST 6994-74 Height of a smoking point flame, mm. - - 25 25 GOST 4338-91 Table 1: Results of the physical and chemical analysis of TC-1 and A-76 oil products according to the state standard specifications GOST 2084-77 and GOST 10227-86 standards. 72 P a g e
Table 2: Results of TS-1 and A-76 oil products of the physical and chemical analysis of various mixes. Mass fraction of A-76 gasoline Characteristic 0,01 0,02 0,03 0,04 0,05 0,06 0,1 0,4 0,6 0,8 0,9 0,95 0,99 the initial 147 145 144 142 140 132 101 79 79 57 48 43 39 I distit 161 159 156 155 154 145 114 98 98 84 77 73 69 10%. I distit 183 181 179 177 175 163 152 148 148 121 117 115 111 50%. I distit 223 223 222 221 220 215 195 191 191 180 178 176 173 90%. Flash point in the 35 33 30 29 26 22 Carrying out analysis dangerously closed cup, 0 C Density 20 0 C, 789,5 789,1 788,7 788,2 787,6 786,9 785,1 774,3 785,5 785,1 756,4 755,8 754,7 kg/m3 Kinematic 1,501 1,484 1,467 1,451 1,442 1,434 1,401 1,114 1,411 1,401 0,629 0,590 0,559 viscosity,20 0 C, cst Boiling temp., 0C Acidity, mg the KOH on 100 cm 3 of fuel 100 cm 3 of fuel Concentration ex. gum, mg on 100 cm 3 of fuel Test on a copper corrosion at 100 0 C Temperature of the beginning of crystallization 0 C Mass share of the general sulfur, % Mass share of merkaptan. sulfur, % Mass share of hydrogen sulfide, % Reid vapour pressure, Kpa Water-soluble acids and alkalis Masses. Share aromat. hydrocarbons. % Height of a smoking point flame, mm. 0,42 0,43 0,45 0,47 0,50 0,52 0,56 0,59 0,65 0,78 0,82 0,91 0,96 0,384 0,383 0,381 0,379 0,376 0,371 0,369 0,344 0,325 0,301 0,258 0,243 0,235 Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. Stab. -68-68 -68-68 -68-68 -68-68 -68-68 -68-68 -68 0,068 0,068 0,067 0,066 0,066 0,065 0,060 0,045 0,038 0,035 0,034 0,033 0,032 0,002 0,002 0,001 0,001 Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. Abs. 21,4 21,6 23,1 23,3 23,9 26,4 28,6 35,8 38,7 40,5 41,9 42,2 43,6 Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. Отс. 16,0 16,2 16,4 16,6 16,8 17,0 17,4 18,6 19,4 20,2 21,0 21,6 22,0 26 28 30 36 40 48 Carrying out analysis dangerously 73 P a g e
experimental data calculated by the rule of additivity Fig. 1: Change, density of mix of oil products TC-1 and A-76 from a mass fraction of A-76 gasoline. 74 P a g e
. experimental data calculated by the rule of additivity Fig. 2: Change, viscosity of Mix of oil Products TS-1 and A-76 depending on a mass fraction of A-76 gasoline. 75 P a g e
1. the initial, 2. I distit 10%. 3. I distit 50%. 4. I distit 90%. - - - - - calculated by the rule of additively Fig. 3: Dependence, Fractional Composition of Mixes of Oil Products TS-1 and A-76 from a mass fraction of A-76 gasoline. 76 P a g e
Zahid Hafeez Khokhar / International Journal of Petroleum and Geoscience Engineering (IJPGE) 3 (4): 161-168, 2015 6. Conclusions In order to have proper results, it is enough to have one or two free tanks for introduction to a zone of contact of the transported oil products of settlement volume of buffer liquid. Similar operations were repeatedly put into practice. The corrected way is to discriminate of oil products with high degree of safety of their quality as material of a buffer stopper is genetically similar to material of the transported oil products allows to carry out consecutive transfer. In particular the way is effective for pumping of oil products with increased requirements to quality, as, fuels for jet engines which mostly are transported now in tanks by rail. Moreover, original the development relating to experiments of receiving buffer traffic jams and their uses for consecutive pumping of aviation kerosene is new. The carried-out is to consider one ASTMD standard or GOST if analyses are carried out by different standards then result GOST R ISO 5725-2-2002 has to answer. The received results on ASTMD and GOST if it is wrong answer GOST R ISO 5725-2-2002 then big technical problems becomes clear. [6] Abdullaev, A. A. B. B., Yufin, V. A., Control in processes of transport and storage of oil products. Subsoil, 264, 1990. [7] Ismayylov, G. G., Nurullayev, V. H., Kelova, I. N., Nurmamedova, R. G., Mixture Influence the raznosortnykh of oil products on their rheological and physical and chemical properties. Fifth International scientific and practical conference, problem of innovative development of the oil and gas industry. Almaty, KBTU, 21-27, 2013. [8] Nurullayev, V. H., Rustamov, M. I., Sultanov, S. A., Receiving RT and A-1 fuels from Azerbaijani nefty by hydrotreating. Azerbaijani oil economy. 48-50, 2001. [9] GOST 2084-77. Fuels motor. Gasoline unleaded. Specifications. [10] GOST 10227-86. Jet fuels. [11] Evdokimov, I. N., Nanotechnological managements of properties of natural oil and gas fluids. MAX. Press, 364, 2010. [12] GOST R İSO 5725-2-2002 Accuracy (correctness and pritsizionnost) methods and results of measurements. Part 2. Main method of determination of repeatability and reproducibility of a standard method of measurements. References [1] Chertkov, Y. B., Motor fuels. Novosibirsk Science, 208, 1987. [2] Bolshakov, G. F., Seraorganicheskiye of compound of oil, Novosibirsk Science, 248, 1986. [3] Lurye, M. V., Maron, V. I., Matskin, L. A., Yufin, V. A., Optimization of consecutive pumping of oil products. Subsoil, 256, 1975. [4] Abuzova, F. F., Bronstein, I. S. V. F., Fight against losses of oil and oil products at their transportation and storage. Subsoil, 248, 1981. [5] Bolshakov, G. F., Restoration and quality control of oil products. Subsoil, 243, 1974. 77 P a g e