CHEMISTRY and TECHNOLOGY of CARBON MATERIALS
Improving the performance properties of automotive motor oils in the development of global requirements and specifications
Keywords: Performance properties, automotive motor oils, global requirements, specification, method of test, engine, emission standards, fuel economy, low speed pre-ignition.
Abstract. The article provides information on the state of development of test methods for automotive motor oils of the last generation and the formation of specifications abroad in the development of global requirements for the performance properties of oils. In this regard, the development of technologies for the development of the oils themselves and the methodology of their testing is relevant. The next stage of reducing emission standards of harmful particles in exhaust gases will come into force
in 2021, and these requirements can presumably be met with oils of modified component composition that meet the requirements of FA-4 category according to API, and have advantages in terms of fuel savings over oils of other categories. Medium-term prospects for reducing emission standards for harmful particles in exhaust gases are planned for 2024, but these norms can presumably be met without upgrading the composition of engine oil by improving the design of the engine and vehicle as a whole.
Emission levels of harmful particles in the exhaust gases by 2027 and will lead to the creation of oils of the new category PC-12. Heavy-duty engine oil will be aimed at higher engine operating temperatures and will provide better wear protection for parts.
Methods based on Ford and General Motors engines have been developed, among other things, for testing oils in accordance with the requirements of the ILSAC GF-6 category, which is accordingly divided into categories GF-6A and GF-6B. The ACEA and ILSAC categories, along with the API, are the most widely used oil standards in the world. Reducing the duration of the methods is a serious problem, given the
complexity of the developing categories, not to mention the investment to develop compositions of new motor oils and support for automakers. Despite the advantages of low-volume, direct-injection and turbo-supercharged gasoline engines (TGDI
engines) in fuel efficiency during their operation, the problem of pre-ignition at low speeds (Low Speed Pre-Ignition — LSPI) arose, which is a significant obstacle to achieving fuel efficiency and CO2 emission standards. The cause of LSPI may also be due to the chemical composition and structure of the detergent and antioxidant additives used in motor oils.
All-Russian Research Institute for Oil Refining [VNII NP], Moscow
Babkin K.D., Makarov A.D.
The development of a mathematical model for determination the anti-knock properties of gasoline with the addition of oxygen-containing octane-increasing additive
Keywords: oxygenates, anti-knock resistance, octane number, methyl-tert-amyl ether, methyl- tert-butyl ether, mathematical model.
Abstract. The necessity of mathematical model for calculation of anti-knock characteristics of oxygenates for their competent planning and involvement in commercial gasoline is proved. The developed model of calculation of the octane number of blending research and motor methods for MTAE and MTBE. High convergence of simulation results and laboratory tests is shown. The contribution of
different classes of hydrocarbons to the intensity of intermolecular interactions in the mixture of oxygenate and base gasoline is described by mathematical methods.
The necessity of mathematical model for calculation of anti-knock characteristics of oxygenates for their competent planning and involvement in commercial gasoline is proved. The developed model of calculation of the octane number of blending research and motor methods for MTAE and MTBE. High convergence of simulation results and laboratory tests is shown. The contribution of different classes of hydrocarbons to the intensity of intermolecular interactions in the mixture of oxygenate and base gasoline
is described by mathematical methods. The necessity of mathematical model for calculation of anti-knock characteristics of oxygenates for their competent planning and involvement in commercial gasoline is proved. The developed model of
calculation of the octane number of blending research and motor methods for MTAE and MTBE. High convergence of simulation results and laboratory tests is shown. The contribution of different classes of hydrocarbons to the intensity of intermolecular interactions in the mixture of oxygenate and base gasoline is described by mathematical methods. The necessity of mathematical model for calculation of anti-knock characteristics of oxygenates for their competent planning and involvement in commercial gasoline is proved. The developed model of calculation of the octane number of blending research and motor methods for MTAE and MTBE. High convergence of simulation results and laboratory tests is shown. The contribution of different classes of hydrocarbons to the intensity of intermolecular interactions in the mixture of oxygenate and base gasoline is described by mathematical methods.
Gubkin Russian state University of oil and gas, Moscow
Investigation resins of products hydrocracking of deasfalted of goudrons
Keywords: hydrocracking, goudron, deasfalte, hydrogenate, resins.
Abstract. The hydrocracking of deasfaltion of goudrons is carried out on molybdena-cobolt- aluminum catalyst at temperatures 400, 425 and 450°C. Hydrocarbon composition of factions of hydrogenizates, boiling away higher 400°С got at the indicated temperatures of hydrocracking, is investigational. It is certain that at the temperature of process of hydrocracking of 450°С at this faction maintenance of heavy aromatic hydrocarbons increased from 3,78 to 25,42% about to comparing to
deasfaltes, and also maintenance of resins went down from 12,57 to 4,62%. Thus at the temperature of process of 450°С maintenance methane-naphthenic hydrocarbons went down considerably. In resins increases nitrogen content extraction from product hydrocracking, but sulfhur and oxygen decreases in comparison with resins of deasfaltes. It is necessary to mark that at this temperature of hydrocracking
faction of hydrogenizates, boiling away higher 400°С was exposed to the most changes.
On the basis of determination of element composition by means of analyzer of Perkin Elmer-240 and molecular mass of cryoscopic method is expect the empiric formulas of resins. The averages of the molecular masses of resins in hydrogenizates are comparatively small and are at the level of 420-503, i.e. diminish with the increase of temperature of hydrocracking. The degree of deficit of protons also diminishes both in resins in initial deasfaltes and in resins of hydrogenizates with the increase of temperature of hydrocracking. On the bases of PMR spectr of is defined higher aromatization resins of hydrogenizates, on the whole production hydrocracking at temperature 450°C. With an increase the temperatures of hydrocracking to
450°С resins, distinguished from hydrogenizates, contain unsubstituted for more protons (from 4,3 to 18,1%) related to the aromatic carbon atoms, and also entering in the complement of groups in .- positions to the aromatic kernels (from 14,5 to the 27,5%) comparing to deasfaltes. In addition, they are characterized by the less stake of atoms of Н in other saturated fragments of molecules more remote from an aromatic kernel. This confirms the higher aromaticity of the hydrogenated resin obtained at a
hydrocracking temperature of 450°C. The calculated data is indicated decrease polycyclic structure of hydrogenate compare with feedstock deasfaltizate molecular resins of hydrogenate included on the average one or two group (block) structure,
including heterocycles, what everyone condense one-two aromatic ring.
The Institute of Petrochemical Processes named after Yu.G. Mamedaliyev, Baku, Azerbaijan
Abbasov V.M., Mammadova T.A., Mammadkhanova S.A., Abbasov A.R.,
Mamedova E.I., Abbasov A.R.
Multifunctional alcohol-essential additives to diesel fuels
Keywords: commercial diesel fuel, ethanol, emulsifier, exhaust gas composition, carboxylic acid esters, propylene oxide
Abstract. As an oxygen-containing additive to diesel fuels, esters of natural carboxylic acids and propylene oxide (CAEPO) have been studied. It was revealed that their addition to the composition of commercial diesel fuel (CDF) to 5% of the mass. allows the improve of the compounds’ quality and the composition of the exhaust gases on their using. For the 5% high-temperature compounds with TDT, the increase in flash point is 3°C, decreasing of freezing temperature is 20°C (to -45°C), also there was
observed the decreasing of coking behavior and the content of aromatic hydrocarbons. Improving the composition of exhaust gases when using 3-5% compounds of the CAEPO with CDF is revealed to the decreasing of carbon monoxide’s content by 20-30%, while reducing the content of sulfur oxides by 0.3- 1.5% mass.
The qualitative indicators of commercial diesel fuel with up to 5% ethanol in it (95% and 99.9% wt) in pure form and with using the CAEPO as a surface-active emulsifier at temperatures 0-25°C, by mixing the mixtures with a speed of 600 rev/min and using an ultrasonic generator UIP2000hd. It was revealed that the use of dehydrated ethanol in the composition of diesel fuel up to 3% mass at room temperature allows to preserve the transparency of obtained compositions within 30 days. The increase of
ethanol content in the composition of diesel fuel up to 5% mass reduces the sustainability of the mixture to 18 days. The decrease of the storage temperature of the obtained compounds to 0 °C leads to the decreasing of stability period of the compounds up to 10-5 days for 1-5% ethanol content in diesel fuel composition, respectively. The using of watered ethanol (95%), even during its 1% content in diesel fuel with using an agitator with turnover speed of 600 rpm an unstable emulsion is formed, which stratifies after a few minutes. However, when mixing the obtained compounds using an ultrasonic sonotrode, slightly coalescing mixtures are forming, the stability of which is no more than 10 days at room temperature and up to 5 days at low temperature. To make the resistant to 3% ethanol mixture, 1% emulsifier was added to the TDT, such as CAEPO. The obtained compound retains the stability for 25 days from the date of preparation. The reduction of carbon monoxide, sulfur oxides and nitrogen in the composition of the exhaust gases of this mixture is 28, 24 and 16%, respectively.
The Institute of Petrochemical Processes named after Yu.G. Mamedaliyev, Baku, Azerbaijan;
Azerbaijan State University of Oil and Industry
Mamedyarov M.A., Gurbanov G.N., Yusiphova L.M.
Alkyl-substituted complex ethers of cyclic polyoles as a basis and component of lubricant oils
Keywords: esterification reaction, cyclic neopolyol ethers, lubricating oils, operational properties, correlation dependence.
Abstract. The esterification reaction of 2,2,6,6-tetramethylolcyclohexanol (TMCH) with aliphatic monocarboxylic acids C С 10,28–10,71 mmС and a viscosity index of 124–135 units, low pour points – -38…-47°C. After determining the thermo- oxidative stability, it was revealed that they have low evaporation (0.33-0.90% by wt.), the amount of
precipitation insoluble in isooctane is 0.002–0.020 wt%. Minor corrosion of aluminum alloy AK-4 (0.009–0.040 mg/cmШХ-15 (0.016–0.060 mg/cm 5-C9 and mixtures of fatty acids fr. C5-C6 were synthesized symmetric and asymmetric esters and studied their physicochemical and operational properties. The synthesized esters are colorless liquids with high boiling points, their yield is 82–90% by weight from the theoretical.
The structure of the synthesized TMCH esters was confirmed by IR and NMR spectroscopy, as well as by determining the molecular weight, acid and ester numbers. When determining the viscosity-temperature properties, they were found to have a viscosity at 100°2/s, high flash points 281–315° 2) and steel 2). After oxidation the acid number of diesters is small 0.15–0.96 mgKOH/g. When determining the lubricity of esters, it was established that they have good lubricating characteristics: wear diameter indicator Di – 0.6–0.8 mm, critical load, Pk – 680–830 Newton. In this work, the correlation relationship between the chemical structure and performance characteristics of the synthesized esters was also studied. When comparing the obtained
results, it can be seen that asymmetric esters are superior to symmetric counterparts in viscosity- temperature and thermal-oxidative and lubricating properties, which are explained by the structure and location of ether groups. As a result of the research, it was found that the esters of 2,2,6,6-tetramethylolcyclohexanol compared
with the esters of pentaerythritol have good viscosity-temperature, thermal-oxidative and lubricating characteristics and can be recommended as a basis and component of new lubricating oils.
The Institute of Petrochemical Processes named after Yu.G. Mamedaliyev, Baku, Azerbaijan
Belov I.V., Likhterova N.M., Volgin S.N., Matin M.E.
Impact of 2-Ethylhexyl Nitrate on Flammability and Lubricity of Fuels Intended
for Jet Engines When Used in Diesel Engines
Keywords: aviation kerosene, diesel fuel, diesel engine, lubricity, flammability, ignition
Abstract. A promising direction for the expansion of diesel fuel resources, especially in the Arctic and the Far North, is the use of aviation kerosene in diesel engines. Due to insufficient ignition and low lubricity of aviation kerosene, their application in a diesel engine is limited. One of the ways to improve the ignition and lubricity of aviation kerosene, when used in a diesel engine, is the adding of cetane and anti-wearing additives applied in industrial production of diesel fuels. The purpose of this paper is to study the effect of 2-ethylhexyl nitrate (ignition activator) on the ignition and lubricity of aviation kerosene when used in a diesel engine. As the objects under study, 14 TS-1 and RT fuel samples produced at Russian refineries were selected: TS-1 straight-run fuels (samples 1-5), TS-1 fuel mixtures (samples 6-10), hydrogenation fuels RT and
TS-1 (samples 11-14). As a result of experimental studies it was found that the adding of ignition promoter at concentration of 0,4% by weight increases the cetane number of all 14 tested samples of TS-1 and RT fuels by 6-8 units. At that time, the lubricity of TC-1 fuel non-containing additives deteriorates, while the lubricity of additive-containing TS-1 and RT fuels increases. The deterioration of the lubricity of TS-1 straight-run fuels up to 12,7% after the adding of 2-ethylhexyl nitrate is due to the presence of heteroatomic (of mercaptans, sulfides) and resinous compounds or adsorption resins, which under the effect of the ignition promoter are oxidized to hydrocarbon-insoluble compounds, and when it enters the friction zone, they intensify the process of abrasive wear, thereby
increasing the value of the diameter of the wear spot. The adding of the ignition promoter into TC-1 fuel mixtures containing both straight-run and
hydrodemercaptanized, hydrotreated and hydrocracked kerosene fractions with antioxidant and anti-wear additives, unlike TS-1 straight-run fuels, enhances the lubricity by an average of 19,2%. Enhancing the lubricity of TS-1 fuel mixtures (samples 6, 8-10) is due to the presence of antioxidant additive in their composition, which interacts with active radicals formed during the decomposition of 2- ethylhexyl nitrate, thereby preventing the acceleration of the liquid-phase oxidation of sulfur compounds
and resinous components. The results obtained for TS-1 fuel mixtures (samples 6, 8-19), similar to RT and TS-1 hydrogenation fuels containing an antioxidant additive (sample 11-14), enhance the lubricity up to 15,5%. Thus, on the basis of the performed experimental studies, it was established that with the adding of different
production technologies of ignition promoter based on 2-ethylhexyl nitrate at concentration of 0,4% by weight into TS-1 and RT fuels, the cetane number increases in a narrow range of values and reaches the required rate while the lubricity of TS-1 straight-run fuels and fuel mixtures, non-containing additives, deteriorates on average by 14,8%, while the diameter of the wear spot reaches the required values.
To ensure the compliance of modified aviation kerosene based on TS-1 and RT fuels to the required level of lubricity, the anti-wear additive application is required.
FAE «The 25 FOR OIL AND PETROLEUM PRODUCTS
Kowalski B.I., Afanasov V.I., Shram V.G.
The study of temperature parameters of the engine oil mixture
th State Research Institute of Himmotology, Ministry of Defence of Russian Federation»
Keywords: optical density, rate of evaporation, an indicator of oxidative stability, the temperature of beginning of oxidation and evaporation, critical temperature.
Abstract. The results of probe of temperature parameters of operability of the Toyota Castle 10W- 30 SL mineral engine oil and its mixture from 20% of partially synthetic Kixx Gold 10W-40 SJ engine oil are presented. Temperatures of the beginning of process of oxidation and evaporation of oils at a termostatirovaniye are determined and critical temperatures of these processes.
Siberian Federal University – Institute of Oil and Gas, Krasnoyarsk, Russian