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USEFUL ADDITIVES FOR PETROL AND OTHER MOTOR FUELS
INVENTION
Patent of the Russian Federation RU2280066

ADDITIVE TO PETROL FUEL

ADDITIVE TO PETROL FUEL

The name of the inventor: Aptekman Alexander Grigoryevich (US); Beklemyshev Vyacheslav Ivanovich (RU); Makhonin Igor Ivanovich (RU); Bolgov Valery Yurievich (RU); Petrov Dmitry Georgievich (RU); Revenko Igor Anatolievich
The name of the patent holder: Limited Liability Company "Laboratory of Tribotechnology"
Address for correspondence: 124460, Moscow, Zelenograd, PO Box 108, Laboratory of Tribotechnology, General Director VI Beklemyshev
Date of commencement of the patent: 2003.12.26

The invention relates to petrochemicals, in particular to additives for motor fuels of the petrol boiling range used in carburettor and injector internal combustion engines. The additive for gasoline fuels contains 17.7-22.4% of the cyclic aromatic compound 1,3-diphenylurea of ​​the formula C 6 H 5 NHCONHC 6 H 5 , 20-22% oxygenates as a mixture of alcohols C 2 -C 5 , 0.1- 0.3% of esters of dicarboxylic acids, 0.02-0.05% of phenol-type ashless antioxidant, and the rest - a solvent in the form of a mixture of kerosene and gasoline. The additive provides an improvement in the combustion regime of various hydrocarbons in the molecular structure and reduces the emission of CO and NO x in the exhaust gases.

DESCRIPTION OF THE INVENTION

The invention relates to petrochemicals, in particular to additives for motor fuels of the petrol boiling range used in carburettor and injector internal combustion engines.

It is known that motor fuels of the petrol boiling range contain various additives, including those intended:

  • To increase the stability of fuel mixtures based on gasoline to detonation with a corresponding decrease in wear of the cylinder-piston group of internal combustion engines;
  • To reduce the toxicity of the exhaust;
  • To reduce the specific costs of motor fuel due to the completeness of the combustion of fuel-air mixtures.

To improve the stability of the petrol fuel boiling range to detonation, reduce the toxicity of the exhaust, use various oxygen-containing organic oxygenate substances, including alcohols (methanol, ethanol, etc.), ethers (methyl tert-butyl, ethyl tert-butyl and others .), As well as other compounds (see AM Danilov "The use of additives in fuels for cars." Reference publication, Moscow, Chemistry, 2000, p.54).

A common disadvantage of oxygenates is the low heat of their combustion with respect to hydrocarbons of the gasoline boiling range, and an increased emission of nitrogen oxides (NO x ) in the exhaust gases (OG).

In view of these circumstances, multicomponent additives are used in motor fuels of the gasoline boiling range, both on the basis of oxygen-containing organic substances of different molecular structure and additives based on oxygenates and other components.

An additive is known for motor fuels of the gasoline boiling range containing oxygenates in the form of C 3 -C 5 alcohols and / or their derivatives, N-methylaniline, ferrocene, aniline, and "AutoMag" additive (RU Patent No. 2132359,1999). This additive is introduced into automobile gasolines in a concentration of 0.2-20% by weight.

The disadvantage of this additive is the presence in it of iron-containing compounds, which, when used in motor fuels, leads to an increase in carbon formation on the candles of the internal combustion engine and additional deposits on the parts of the cylinder-piston group.

A multifunctional additive for motor petrol of a gasoline boiling range containing N-methylaniline, C 3 -C 5 aliphatic alcohols, an amide-based detergent additive, antioxidants in the form of 2,6-di-tert-butyl-4-methylphenol or a solution of a mixture of screened phenols In toluene, ethyl ether (Eurasian patent No. 000882, 2000). Additive is introduced into automobile fuel.

The disadvantages of this additive and the fuel containing it are:

  • The need to use a stabilizer in the form of aliphatic alcohols C 3 -C 5 , increasing the cost of the additive;
  • Relatively low antiknock detonation efficiency;
  • Insufficient chemical stability of the composition during storage.

To increase the detonation resistance of automotive gasolines, to reduce the oxidation of the composition during storage, an additive containing an aromatic amine (R 3 C 6 H 4 -NR 1 R 2 ), an oxygenate (R 4 -OR 5 ) and hydrazine at a weight ratio of aromatic amine: oxygenate components : Hydrazine = (0.5-70): (93.5-29.995): (0.005-2) (patent RU No. 2184767, 2002).

The use of aromatic amines in motor gasolines increases their detonation resistance.

At the same time, aromatic amines have an increased tendency to gum on the parts of the cylinder-piston group, which increases the wear of the latter, and does not contribute to reducing the emission of nitrogen oxides (NO x ) in the exhaust. The use of a significant amount of oxygenate in this additive will lead to a significant increase in the emission of these gases in the exhaust gas, which is significant for the urban driving regime.

In addition, with the process of progressive cracking typical for the combustion chamber of the engineered hydrocarbons that are different in the molecular structure of the fuels, the effect of aromatic amines on the combustion process as a whole is not significant because of their insufficient thermochemical resistance.

Composite additives for gasoline boiling point motor fuels are known which are designed to reduce the formation of CO, CH and NO x emissions and simultaneously contribute to the equalization of the temperature field in the dvc cylinders, thereby improving the combustion of various molecular hydrocarbons (WO No. 96/40844, RU Patent No. 2,187,541).

The additive of RU Patent No. 2,187,541 contains at least one copper compound with an ionic bond, at least one zinc compound with an ionic bond, with one mole of copper containing 0.03-0.7 mole of zinc and further comprising , At least one organic substance, for example from the group consisting of oxyquinoline, cupferon, neocupferone, and an arbitrary complexone from a variety of aminopolycarboxylic acids, which dissolve the metal salts in the hydrocarbons of the fuel.

This additive has a clearly pronounced drawback in terms of its multicomponence and the need to select the arsenal of components, taking into account the specificity of the given compounds to a certain composition of used fuels, which increases the cost of the additive and limits its use for liquid fuels of a gasoline boiling range with arbitrary chemical composition.

The closest analogue of the claimed technical solution is an addition to the motor fuel of a gasoline boiling range containing cyclic aromatic compounds in the form of polyunsaturated aliphatic or acyclic compounds with double bonds (vitamin A), derivatives of dihydrobenzo U -pyrans (vitamin E), and polyoxyethylene (polyethylene glycol , Polypropylene glycol, sorbitol), fatty acid esters (US Pat. No. 6,482,243, 2002)

The additive is used in motor fuels of the gasoline boiling interval in an amount of 1 part per 500-1500 parts of fuel.

The disadvantages of this additive are:

  • Complexity of composition composition;
  • Energy-chemical storage instability due to the presence of components such as vitamins A (retinol) and E (tocopherol);
  • A complicated process of synthesis of molecular structures of these vitamins.

The aim of the invention was to expand the arsenal of highly effective, simple composite additives for motor petrol of the gasoline boiling range, which provide an improvement in the combustion regime of hydrocarbons that are different in molecular structure and reduce the emission of CO and NO x in the exhaust gases.

To solve the above problem, an additive for gasoline fuels containing a cyclic aromatic compound and oxygenates in the form of a mixture of C 2 -C 5 alcohols and dicarboxylic acid esters is proposed. According to the invention, 1,3-diphenylurea of ​​the formula C 6 H 5 NHCONHC is used as the cyclic aromatic compound 6 H 5 , the additive further comprises an ashless antioxidant of the phenolic type and a solvent in the form of a mixture of kerosene and gasoline in the following ratio, by weight:

1,3-diphenylurea 17.7-22.4
Alcohols C 2 -C 5 20-22
ester
Dicarboxylic acid 0.1-0.3
Antioxidants 0.02-0.05
solvent rest

According to the invention, esters of adipic acid, adipic acid dibutyl ester, phthalic acid dibutyl ester, sebacic dioctyl ester, azelaic acid dioctyl ester, dibutyl phthalate or a mixture thereof are used as esters of dicarboxylic acids.

According to the invention, dibutyl ester of phthalic acid or dioctyl ester of sebacic acid or / and dioctyl azelaic acid or mixtures thereof are used as esters of dicarboxylic acids.

According to the invention, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, ester of b - (3,5-di-tert-butyl-4 -hydroxyphenyl) -propionic acid with octadecanol or 1,6-hexanediol.

According to the invention, 2,6-di-tert-butyl-4-methylphenol is used as ashless phenolic type atioxidants.

According to the invention, a mixture of kerosene and gasoline is used at a ratio of (0.5-1) :( 1.0-2.0) (c.s.).

When using additives in motor fuels of the petrol boiling range, combustion of fuel and air charges in the combustion chambers of carburetor and injector engines is improved and the emission of CO, NO x gases is reduced, which is explained by:

  • The presence of 1,3-diphenylurea (C 6 H 5 NHCONHC 6 H 5 ) in the molecule of a large number of p- electrons connected in a single conjugated system. These electrons have great mobility, so the DFM molecule slopes to strong polarization as it approaches charged particles (ions) of the flame plasma, charging like an electric capacitor. The plasma ions condensed around polarized molecules increase the energy of the combustion plasma;
  • The propensity of the molecular structure of 1,3-diphenylurea (C 6 H 5 NHCONHC 6 H 5 ) at elevated temperatures to reduce nitrogen oxides to pure nitrogen;
  • To facilitate the combustion of fuel hydrocarbons to non-toxic CO 2 due to the stability of the temperature field in the combustion chamber.

The presence of antioxidants in the composition, as well as the use of a solvent for the preparation of a solvent additive in the form of a mixture of liquid hydrocarbons of kerosene and gasoline, ensures the stability of preserving the chemical-physical properties of the additive over a long period.

The additive composition proposed according to the claimed technical solution is selected from the group of simple and accessible chemical compounds. The additive improves the burning regime of various liquid hydrocarbons in the molecular structure, ensures the completeness of their combustion, which reduces the specific costs of motor fuel, lowers CO and NO x emissions, reduces tar formation, and decreases the wear of the cylinder piston group.

In the analysis of the prior art, no additives for motor fuels of the gasoline boiling range have been identified with a set of features corresponding to the claimed technical solution and realizing the above-described technical result, which is confirmed by the following description of the invention.

The essence of the invention is explained by recommendations on the selection of raw components, examples of specific compositions of composite additives, recommendations for their practical application and test results.

For the preparation of specific compositions of additives for fuel gasoline boiling range used in carburetor and injector internal combustion engines, ready-to-use raw materials are used.

For specific additive compositions according to the invention, the following are used:

  • 1,3-diphenylurea (C 6 H 5 NHCONHC 6 H 5 ), m.p. - 212.25, T bp. - 262 ° C (Catalog Handbook of Fine Chemicals Aldrich, 1992-1993, 250 p.);
  • Isopropyl alcohol, sec-butyl alcohol;
  • Esters of dicarboxylic acids - dibutyl ester of phthalic acid (C 6 H 4 (COO 4 H 9 ) 2 , dioctyl ester of sebacic acid ((CH 2 ) 8 (COOC 8 H 17 ) 2 ) The named esters of dicarboxylic acids in the preparation of additive compositions Are chosen in the ratio 1: 1;
  • Ashless antioxidant phenolic type -2,6-di-tert-butyl-4-methylphenol. The trade mark "Agidol" -TU 385901237-90;
  • Kerosene-TU-3840158-10-90. It is possible to use kerosene TS-1-GOST 10227-86;
  • Trade in vitamins retinol and tocopherol;
  • Gasoline of the trade mark AI-92.

From the raw materials used, within the preset formulations, by mixing at room temperature, 500 ml of ready-made additive compositions were prepared according to the following examples:

Example 1 - Additive according to the invention:

1,3-diphenylurea - 90 g, isopropyl and sec-butyl alcohols in a ratio of 1: 1 to 100 ml, a mixture of dicarboxylic acid esters (phthalic acid dibutyl ester, sebacic acid dioctyl ester at a ratio of 1: 1 (bw) - 1 ml, 2,6-di-tert-butyl-4-methylphenol - 0.15 ml, kerosene 100 ml, petrol AI-92 - the rest.

Example 2 is an additive with the composition of components of US Pat. No. 6,482,243:

Retinol and tocopherol at a ratio of 1: 1 (c.ch) - 50 ml; Isopropyl and sec-butyl alcohols in a ratio of 1: 1, said mixture of esters of dicarboxylic acids at a ratio of 1: 1 (cc) to 450 ml.

Example 3 - automobile gasoline AI-92.

To study the effect of additive compositions on the operation of an internal combustion engine, the additives indicated in Examples 1 and 2 were in an amount of 0.2% by weight introduced into AI-92 automobile gasoline. The specified norm on the use of additives in finished gasoline fuels corresponds to the known recommendations.

When studying the effect of the additives specified in Examples 1 and 2 on the operation of the internal combustion engine, the following methods were used.

1. One of the cylinders of the engine (4-cylinder, with distributed fuel injection, volume 2000 cm 3 , compression ratio 9.8) was equipped with a specially modified spark plug with a piezoelectric sensor that allows to convert the pressure fluctuations in the cylinder into an electrical signal, which in Digitized form was subjected to processing methods of discrete transformation and dynamic spectral analysis, allowing to track the appearance and attenuation of frequency components with a maximum resolution of 1 Hz.

2. Measurement of the content of carbon monoxide (CO), hydrocarbons (СН) and nitrogen oxides (NO x ) in exhaust gases (OG). The measurements were carried out on the cars "Niva" and "Toyota-Vista" (distributed fuel injection). The content of CO and CH was determined using a portable gas analyzer, the NO x content by iodometric method from a solution of potassium iodide through which a certain volume of exhaust gas was passed. The measurements were carried out at different operating conditions of the engine.

3. Road tests were carried out on the cars "Niva", "Toyota-Vista", VAZ-2106, UAZ-469, GAZ-53, Volga GAZ-24.

Based on the data obtained during the acoustic analysis of the processes in the cylinder of the engine based on the time of echo signals reflected from the piston, and the data on the temperature values ​​of the exhaust gases at the time of release, the values ​​of the sound velocities at different moments of the compression-expansion cycle were calculated for which Pressure values ​​in the cylinder for various operating modes. As can be seen from the diagram 1 below (see Fig. 1):

  • When using an additive (example 1) in gasoline, the useful work of the expanding gas (curve 1) with an equal fuel consumption increases (the area bounded by the pressure curve of the 4-stage compression and the 1-stage expansion curve) by approximately 25%;
  • When using the additive (example 2), the indicated indices (curve 2) practically correspond to the use of commercial gasoline in the internal combustion engine (curve 3).

The changes in torque in the internal combustion engines (diagram 2, Fig. 2) are similar in the values ​​obtained.

The results obtained from the diagrams 1-2 have a similar tendency when the ratio of the raw material components according to the claimed additive varies within the given formulation (mass%).

Decrease in the composition of 1,3-diphenylurea leads to a decrease in the obtained technical parameters in diagrams 1-2. The increase in the additive formulation of this compound does not have a significant effect on the thermal process of the engine operation.

In view of these circumstances, it has been established that it is expedient to use the claimed additive in motor gasoline within known recommendations, but at a concentration of not more than 1%.

The decrease or increase in the additive formulation of a given ratio of aliphatic alcohols, dicarboxylic acid esters can, on the one hand, lead to a decrease in the detonation resistance of the fuel, on the other hand, to an increase in the emission of nitrogen oxides.

The decrease in the additive formulation of a given amount of antioxidant affects the thermochemical resistance of the composition when used in the latter mentioned solvents. The increase in antioxidants increases the cost of the additive.

The use of a solvent based on a mixture of liquid hydrocarbons, respectively, kerosene and gasoline, is most suitable for the technological compatibility of the additive composition with motor gasolines. The ratio of kerosene to gasoline according to the invention corresponds, on the one hand, to the requirements of fire safety, and on the other hand, it is most optimal for the conditions of use of the additive in commercial gasolines

Studies and confirmed that the chemical-physical properties of the additive in relation to commodity gasoline are stable for a long period (over 3 months). Tests of the additive containing retinol and tocopherol after 20 days of storage of this additive showed that the technical parameters when using gasoline with this additive correspond to the indices of commercial motor gasoline without this additive.

The phenomenon resulting from the use of the additive according to the invention is explained by the following:

At the initial stage of combustion, the process proceeds through a branched chain mechanism until the temperature in the cylinder reaches a critical value at which ionization of the gas starts, accompanied by energy costs and some stabilization of temperature and pressure (points 4.1, 4.2, 4.3 - diagram 1).

In the presence of an additive (example 1), the ions of gas components formed during the ignition of hydrocarbons concentrate around the polarized molecules of diphenylurea, which shifts the equilibrium and facilitates the further ionization of the gas. A significant fraction of the energy released during combustion passes into the potential energy of bound charges. As the pressure in the cylinder decreases (curve 1), the stored energy is released when the piston is operated (expansion section), the pressure on the piston decreases less sharply, the efficiency and torque increase (curve 1.1 - diagram 2).

Since the combustion of fuel occurs in a very short period of time, most of the additive molecules, which have significant chemical resistance, do not have time to break even at such high temperatures, the additive burns down after. This fact is also confirmed by the fact that if there is an additive (example 1), the pressure jump at the moment of burning develops less sharply, which is revealed when reproducing unprocessed sound files recorded directly from the sensor, while slowing the playback speed by 32-64 times.

Another feature of the inventive additive (example 1) is its ability to react with nitrogen oxides to form molecular nitrogen, water and carbon dioxide.

The argument for the idea of ​​the participation of the additive in the combustion processes in molecular form is a sharp decrease in the concentration of nitrogen oxides in the exhaust gases with the addition of the additive to the fuel.

Thus, when the Toyota-Vista car engine is running unloaded at 1000 rpm, the addition of an additive (Example 1) to 0.2% gasoline results in a drop in NO x content of 0.4 mg / m 3 To a value less than the detection limit (0.01 mg / m 3 ). The content of carbon monoxide (CO) and hydrocarbons (СН) decreases. The degree of this decrease depends on the operating mode of the engine and reaches a 6-fold value for CO and a 14-fold for SN at 2000 rpm without load (Toyota Vista without a catalytic afterburner filter).

Road tests on various cars, various gasolines in the summer, autumn and winter periods while driving through the city and along the highway allow us to draw the following conclusions:

When inspecting engine parts and assemblies that have worked more than 5000 km of run with the additive according to the invention of any signs of negative influence, no additive for the engine has been detected;

When using the additive of the invention, the sensitivity of the engine to changing the ignition timing is lowered. This allows you to switch to less quality gasoline without significant reduction in power and increased flow. When carrying out road tests on the Volga cars GAZ-24, Moskvich 412, GAZ-53, UAZ-469 with straight-run gasoline (BGS, octane number-65 according to the motor method), there were no significant differences between the BGS and the additive from commercial gasoline AI-80. And tests were carried out with an additive on the car VAZ-2106. In this case, the installation of a later ignition allows to eliminate the detonation without a noticeable loss in power.

CLAIM

An additive for gasoline fuels containing a cyclic aromatic compound and oxygenates as a mixture of C 2 -C 5 alcohols and dicarboxylic acid esters, characterized in that 1,3-diphenylurea of ​​the formula C 6 H 5 NHCONHC 6 is used as the cyclic aromatic compound H 5 , the additive further comprises an ashless antioxidant of a phenolic type and a solvent in the form of a mixture of kerosene and gasoline in the following ratio, by weight:

1,3-Diphenylurea 17.7-22.4
Alcohols C 2 -C 5 20-22
Ester
Dicarboxylic acid 0.1-0.3
Antioxidants 0.02-0.05
Solvent Rest

2. An additive according to claim 1, characterized in that as esters of dicarboxylic acids, adipic acid esters, adipic acid dibutyl ester, phthalic acid dibutyl ester, sebacic dioctyl ester, azelaic acid dioctyl ester, dibutyl phthalate or a mixture thereof.

3. An additive according to claim 2, characterized in that as dicarboxylic acid esters, dibutyl ester of phthalic acid or dioctyl ester of sebacic acid and / and dioctyl ester of azelaic acid or mixtures thereof.

4. An additive according to claim 1, characterized in that 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, ester b - (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with octadecanol or 1,6-hexanediol.

5. An additive according to claim 4, characterized in that 2,6-di-tert-butyl-4-methylphenol is used as ashless phenolic type atioxidants.

6. The additive according to claim 1, characterized in that it contains a mixture of kerosene and gasoline at a ratio of (0.5-1) :( 1.0-2.0) (c.).

print version
Date of publication 07.04.2007gg