RU2547151C1 - Non-ethylated aircraft gasoline - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a composition of aircraft non-ethylated gasoline, which contains gasoline of catalytic reforming, alkylgasoline, toluene and an antiknock additive, and the composition additionally contains a gasoline fraction, boiling out in ranges of 62-85°C, and as the antiknock additive - monomethylaniline and methyltertbutyl ether with the following component ratio, wt %: alkylgasoline 15.0-25.0; toluene 10.0-20.0; gasoline fraction, boiling out in the range of 62-85°C, 20.0-35.0; monomethylaniline 1.5-3.0; methyltertbutyl ether 5.0-10.0; catalytic reforming gasoline - the remaining part.

EFFECT: reduction of the toxicity of the non-ethylated aircraft gasoline without the deterioration of exploitation properties, regulated by the GOST requirements 1012-72, with the simultaneous extension of the nomenclature of piston engines of internal combustion of the domestic and foreign production, using aircraft gasoline.

3 tbl

Description

The invention relates to liquid hydrocarbon fuels, in particular to aviation unleaded gasolines that contain anti-knock additives, and can be used in aircraft with piston aircraft engines.

According to federal law No. 34-FZ “On the Prohibition of the Production and Turnover of Leaded Motor Gasoline in the Russian Federation”, the production of domestic aviation gasoline was discontinued on the territory of the Russian Federation on July 1, 2003 due to the lack of development of a domestic antiknock additive based on tetraethyl lead. To ensure the operation of military aircraft with piston aircraft engines, foreign aviation gasoline B 91/115 (WT-06 / OBR PR / PD / 60) produced by the SIC of the oil refining industry, Plock (Poland) is supplied to the federal structures of the Russian Federation, and for small Aviation DOSAAF - European leaded aviation gasoline 100 LL manufactured in the Netherlands. This circumstance negatively affects the energy independence of the state, as it makes it dependent on imports of products of countries participating in the NATO bloc.

Aviation gasolines intended for use in piston aircraft engines must ensure their normal operation in all operating modes. In accordance with existing requirements of GOST 1012-72 “Aviation gasolines. Technical conditions ”they should have the necessary detonation resistance on a poor and rich air-fuel mixture, optimal fractional composition, low crystallization temperature, low content of resinous substances and sulfur compounds, high heat of combustion and chemical stability during storage.

The conditions for the use of aviation gasolines in an aircraft engine differ significantly from the use of automobile gasolines in an automobile engine, namely:

- sharp changes in atmospheric pressure during the evolution of aircraft along the echelons of heights;

- significant engine operating time at maximum mode (afterburner) - up to 30 minutes of continuous engine operation afterburning;

- higher fuel consumption (0.8-2.2 times) compared with gasoline;

- a higher degree of compression in the cylinders of aircraft engines;

- high thermal stress of the aircraft engine (up to 280 ° C).

In accordance with the requirements of GOST 1012-72, the Russian oil refining industry produced aviation gasoline grades B-91/115 and B-95/130. The most popular of these was B-91/115 gasoline, in which tetraethyl lead (TES) was widely used as an antiknock, the unique antiknock properties of which were discovered by specialists of General Motors Research Corp in 1921. Adding tetraethyl lead to aviation gasoline was the cheapest and the most common way to increase the detonation resistance of aviation gasoline and its grade.

The ban on the use of ethyl fluid (compositions based on tetraethyl lead) entailed many problems:

- lost production of aviation gasoline due to the lack of production of thermal power plants;

- reduction in the number of flight hours of flight of aviation military equipment due to the lack of alternative technologies for the production of aviation gasoline;

- search for other antiknock agents - replacement of thermal power plants.

The authors were faced with the task of developing a new unleaded aviation gasoline that would meet the following requirements:

- have an affordable commodity base;

- have a cost of not more than 120,000 rubles / t;

The operational properties of the new unleaded aviation gasoline should be no worse than the requirements for the operational properties of aviation gasoline in accordance with GOST 1012-72.

According to GOST 1012-72, aviation gasolines are made from products of direct distillation of oil boiling in the range of 30-85 ° C, with an octane number according to the motor method 60-75, catalytic cracking (processing of fractions boiling in the range of 350-540 ° C) with an octane number according to the motor method 90-92 with the addition of high-octane components - alkylate, isomerizate, technical isooctane, ethyl fluid and antioxidants [Chulkov PV, Chulkov IP A Brief Dictionary of Petroleum Products. - M .: Polytechnic, 1997 - p.16.17].

It is also known that B-92 grade gasoline with a low ethyl fluid content was produced according to TU 38.401-58-47-92. But due to the above reasons, there is no production of this gasoline in the country.

Recently, the base component for the production of B-92 and B-91/115 grade gasolines has been catalytic reforming gasolines. Alkylbenzene, isooctane, isopentane and toluene are used as high-octane components.

Also known is a composition of aviation gasoline with an octane rating of at least 91 and a rating of at least 115 based on motor gasoline, containing, wt.%:

mixture of isoparaffin hydrocarbons C ₆ -C ₈ 15-40 hydrogenated fraction With ₆ residual content benzene no more than 3 wt.% to 10 TPP 0.15-0.35 gasoline with an octane rating of at least 92 research method up to 100

TPP is contained in a solution of C6-C8 isoparaffin hydrocarbons, or in ethyl liquid, or in a mixture thereof in the indicated amount.

(Patent No. 2503711, C10L 1/06 2012)

However, this aviation gasoline composition has the following disadvantages:

- the composition is toxic due to the presence of TPP;

- the production and use of aviation gasolines from thermal power plants in the Russian Federation is prohibited (No. 34-FZ);

- Lack of production of thermal power plants in the Russian Federation.

The closest to the invention in technical essence and taken as a prototype is aviation gasoline brand B-91/115 GOST 1012-72, containing catalytic reforming gasoline, alkylbenzene, toluene and an anti-knock additive - ethyl liquid based on TPP, in the following ratio of components,% mass . [V.A. Piskunov, V.N. Zrelov et al. Chemotology in civil aviation. - M .: Transport, 1983. - p.65]:

catalytic reforming gasoline 50-55 alkyl benzene 35-40 toluene 10-15 antiknock additive ethyl liquid R-9 based on TPP 1.5-2.5

The main disadvantage of this aviation gasoline is its high toxicity due to the presence of ethyl fluid, which served as the cancellation of the production of this aviation gasoline, in addition, gasoline has a high cost.

The technical result of the invention is to reduce the toxicity of unleaded aviation gasoline without compromising the performance properties regulated by the requirements of GOST 1012-72, while expanding the range (list) of reciprocating internal combustion engines of domestic and foreign production using aviation gasoline.

The specified technical result is achieved by the fact that the known composition of aviation unleaded aviation gasoline containing catalytic reforming gasoline, alkylbenzene, toluene and an antiknock additive according to the invention additionally contains a gasoline fraction boiling in the temperature range 62-85 ° C, and monomethylanline as an antiknock additive and methyl tert-butyl ether in the following ratio of components,% mass .:

alkyl benzene 15.0-25.0 toluene 10.0-20.0 gasoline fraction boiling in the range temperature 62-85 ° C 20.0-350 monomethylaniline 1.5-3.0 methyl tert-butyl ether 5.0-10.0 catalytic reforming gasoline rest

Alkylbenzene is a mixture of isoparaffin hydrocarbons, mainly C ₆ -C ₉ , obtained by alkylation of industrial isobutane with n-butylenes (usually at 0-10 ° C in the presence of concentrated H ₂ SO ₄ or at 25-30 ° C in the presence of HF acid or AlCl ₃ ). The main components - (up to 60%) - isooctane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane. Liquid. Boiling point T _bale = 40-180 ° C, density 0.690-0.710 g / cm ³ , iodine number 0.35-0.50. It is used to increase the octane number of gasolines, grade - 140-155. Has a commodity base [Petroleum products: Handbook / Ed. B.V. Losikova. M.: Chemistry, 1966 - p. 99].

Petroleum toluene (GOST 14710-78) is obtained in the process of catalytic reforming of gasoline fractions, as well as in the pyrolysis of petroleum products, intended as high-octane additives to motor fuels, as a solvent. Toluene is a colorless transparent liquid, density ρ = 865-867 kg / m ³ , the octane number according to the motor method is 103 [Petroleum products: Handbook / Ed. B.V. Losikova. M .: Chemistry, 1966 - p.78].

The gasoline fraction boiling in the temperature range 62-85 ° C is a straight-run basic component of gasoline with an octane number according to the motor method 70-75. The composition of the fraction: naphthenic hydrocarbons - 55-60 wt.%, Paraffin - 36-41 wt.%, Aromatic - up to 4 wt. Has a wide production base in Russia [A.A. Gureev, B.C. Azev. Car gasoline. Properties and application. - M .: Oil and gas, 1996 - p.86].

Monomethylaniline is produced according to TU 2471-269-00204168-95 and is a compound with a purity of at least 93%. Monomethylaniline is an oily transparent yellow liquid. A reddish tint is allowed. Density ρ = 960–975 kg / m ³ , boiling temperature T _bales = 482 ° С, flash point T _pop = 86 ° C, calorific value 38220 kJ / kg. The maximum permissible concentration in the air is 0.1-0.16 g / kg of air. It is used to increase the octane number in gasoline. It has a wide production base in Russia [AM Danilov. Additives and additives. Improving the environmental performance of petroleum fuels. - M .: Chemistry, 1996 - p.102-104].

Methyl tert-butyl ether is a colorless liquid with a pungent odor, density ρ = 740 kg / m ³ , boiling point T _bale = 55 ° C, flash point T _bp = minus 28 ° C, calorific value 38,220 kJ / kg, octane number according to the motor method - 110, the octane number according to the research method - 125. The maximum permissible concentration in gasoline is 10%, it is used to increase the octane number in gasoline, has a wide industrial base in the country, and is medium toxic [AM Danilov. Additives and additives. Improving the environmental performance of petroleum fuels. - M .: Chemistry, 1996 - p. 41, 95, 103, 105].

Catalytic reforming gasoline - gasoline obtained as a result of aromatization of feedstock by dehydrocyclization of paraffins, dihydroisomerization of alkylcyclopentanes, dehydrogenation of cyclohexanes, isomerization and hydrocracking. As a result, the straight-run fraction (feedstock) is converted to high-octane gasoline with an octane number according to the motor method 80-83. The density of gasoline is 760-780 kg / m ³ . The content of aromatic hydrocarbons - 52-61% by weight, naphthenic and paraffin - 37-45% by weight, is used for the manufacture of high-octane commercial gasoline, has a wide production base in the country [A.A. Gureev, BC Azev. Car gasoline. Properties and application. - M .: Oil and gas, 1996 - p.69-72].

Thus, the qualitative composition of aviation gasoline is a product obtained on the basis of components manufactured in the Russian Federation, which naturally reduces the cost of production.

Despite the fact that the components used are widely known in terms of quantity, it was necessary to conduct research on the selection of the composition so that the resulting gasoline would meet the requirements of GOST 1015-72 in terms of the physicochemical parameters of this GOST.

To substantiate the quantitative component composition of unleaded aviation gasoline, samples were prepared, the composition of which is presented in table 1.

The prepared samples were tested in accordance with the requirements of GOST 1012-72. The results are presented in table 2.

As can be seen from the test results of the samples, only in the claimed range the amount of component content is achieved normalized values of physico-chemical parameters.

According to sample No. 3, which has optimal values, an experimental batch was prepared, which was tested for compliance with the requirements of GOST 1012-72 (table 3).

Thus, the application of the invention will reduce the toxicity of unleaded aviation gasoline without compromising performance, regulated by the requirements of GOST 1012-72, while expanding the range (list) of reciprocating internal combustion engines of domestic and foreign production.

Claims (1)

The composition of aviation unleaded gasoline containing catalytic reforming gasoline, alkylbenzene, toluene and an antiknock additive, characterized in that it further comprises a gasoline fraction boiling in the range of 62-85 ° C, and as an antiknock additive - monomethylanline and methyl tert-butyl ether in the following ratio of components, % mass .:
alkyl benzene 15.0-25.0 toluene 10.0-20.0 boiling gasoline fraction in the range of 62-85 ° C 20.0-35.0 monomethylaniline 1.5-3.0 methyl tert-butyl ether 5.0-10.0 catalytic reforming gasoline rest