RU2305125C9 - Antiknock gasoline additive - Google Patents

Abstract

FIELD: liquid fuel additives.

SUBSTANCE: additive contains (i) mixture of alkoxy-substituted benzenes of general formula:

(I) wherein R represents ethoxy or methoxy radical and (ii) aniline at their ratio 1:1.

EFFECT: considerable increased antiknock effect.

6 ex

Description

The present invention relates to additives that increase the anti-knock resistance of hydrocarbon fuels (fuels, gasolines), and can be used in the field of oil refining, gas processing to create high-octane fuels.

With the advent of internal combustion engines operating at high compression ratios, the problem of increasing the octane number of hydrocarbon fuels (fuels) arose.

It is known that the octane number of fuels increases with an increase in the content of branched and unsaturated hydrocarbons and aromatic hydrocarbons in the fuel. Continuous development and improvement of aviation and automotive technology requires the creation of new high-octane fuels.

This problem can be solved by creating new chemical processes for reforming direct gasoline, catalytic cracking and catalytic reforming or adding special antiknock additives (additives) and high-octane components to hydrocarbon fuels (fuels). In this case, a synergy effect may occur.

The most technologically and economically advantageous is the use of high-octane hydrocarbon combustible antiknock additives.

It is known that to increase the octane number of fuels, both ash and ashless antiknock additives (additives) and oxygenates are used (used).

The well-known ash antiknock additives (additives) used to date are organic compounds of manganese, iron, copper, chromium, cobalt, nickel, rare earth elements, lead, etc.

However, all of them are highly toxic, especially organic lead compounds, both themselves and their combustion products, and have a negative effect on the operation of internal combustion engines, accumulating on the electrodes of spark plugs, pistons and walls of the combustion chamber, significantly reducing its life [1].

Ashless antiknock additives (additives), although less effective than ash ones, are more widely used and used, especially in combination with other components.

The most famous and common ashless antiknock additives (additives) are: low molecular weight aromatic amines [N-methylaniline (MMA), xylidine, toluidine].

The known additive is Extralin TU 6.02.571-90, containing in percent mass ratios dimethylaniline up to 4.5%, aniline up to 6% and N-methylaniline up to 100%.

Another known additive of a similar type is the ADA additive TU 38-401-58-61-93, which additionally contains an antioxidant additive like ionol.

The disadvantages of this type of additives is their restriction in content due to the increase in oxidation products in fuels, gum formation during storage, and carbon formation during operation in engines with their increased concentration and relatively low increase in the octane number of fuels.

It is known to use esters and alcohols as oxygenates, as well as mixtures thereof, to increase the detonation resistance of fuels [2].

The most famous and used oxygenates are methyl or ethyl tert-butyl ethers (MTBE, ETBE), diisopropyl ether, among n-butyl, isopropyl, ethyl, methyl alcohols.

The disadvantages of such additives are a slight increase in the octane number of gasolines with a high content of them and a negative effect on the rubber, polymer and metal parts of the car, and a decrease in the energy consumption of gasolines.

However, the widespread use of oxygenates with high octane mixing ratios in the composition of fuels makes it possible to reduce the octane requirements of the resulting gasoline fractions and provides flexibility in oil refining schemes at oil refineries and to reduce capital investments in oil refining.

The present invention solves the issue of expanding the range of oxygenates to increase the raw material base, the possibilities of creating fuel compositions with desired properties.

It is known that hydrocarbon fuels (fuels) consist of a mixture of various hydrocarbons, which, with a certain combination of components, can acquire the necessary properties in the process of their use (application), namely, as hydrocarbon fuels (fuel) in internal combustion engines, where their optimal operation requires simultaneous achievement of the maximum pressure of the vapor-air mixture at the moment the piston passes the top dead center and decomposition (ignition) of this mixture from the electric spark of the spark plug. If these conditions are not met, detonation occurs, which adversely affects engine operation, fuel consumption and exhaust gas composition.

It is well known that the properties of compounds depend mainly not only on the elements that make up their molecules, but also on the relative positions of these elements or groups of atoms of elements with respect to each other, and also due to which bonds their association in the molecule of substance passes, there is a design of molecules, their composition and type of bonds in them in a certain way affect the physical and chemical behavior of substances (compounds), both intramolecular and intermolecular, including the interaction between molecules of different substances (compounds), which in turn can significantly affect the properties of the entire system as a whole.

Alkoxy substituted benzenes can, in combination with hydrocarbon fuels (fuels) consisting of a mixture of various hydrocarbons, form intermolecular bonds with the molecules of the substances that make up the fuels through the formation of complexes with charge transfer, π-complexes, σ-complexes, as well as free stable radicals and other active intermediates with resonant energy exchange or new formations, which determines the possibility of a synergistic effect.

The system can be excited by various and numerous factors at the same time or selectively from only one factor, for example, from an electric discharge, which is very important when certain processes occur under given conditions.

To regulate such processes, such compounds (substances) are used (the excitation of molecules of which can occur only from one particular factor (electric spark), and transfer the excitation is sensitized to the entire system and at the same time inhibit other factors that prematurely affect this process, for example high-temperature effects (thermal effects) on the system, which is the determining condition for the optimal operation of internal combustion engines.

Such a theoretical justification makes it possible to implement the right approach to solving a number of issues, for example, such as selection of components of fuel compositions in order to obtain the required qualities (high octane number, reduction of oxidative processes and gum formation, etc.).

It is known to use anisole (methoxybenzene and / or its derivatives as an antiknock additive to gasoline [3, 4].

The use of phenethol (ethoxybenzene) for the same purpose is known [5]

The use of aniline as an antiknock additive is known [6].

Analogs in this case can be oxygenates, aromatic amines, mixed additives based on aromatic amines and oxygenates.

The disadvantages of oxygenates are the need to add them in gasoline in large quantities of 10-25% to raise the octane number by 3-8 units, while reducing the energy of fuels and increasing the negative impact on the rubber parts of cars [2].

The disadvantages of additives containing aromatic amines are their instability, the need for their use in combination with antioxidants, fuel compositions with their use are characterized by increased gumming, as a result of which the permissible concentration of aromatic amines in the fuel is limited to 1-1.3 wt.%.

Closest to the technical nature of the proposed solution is the additive ODE-M grade A (composition ODE-M grade A - 80 wt.% Methanol and 8-16.6 wt.% N-methylaniline) [2].

The disadvantage of this additive is a slight increase in the octane number of 4 units. with the introduction of 5 wt.% in the reference mixture, instability and increased gumming when introduced into the fuel in high concentrations, lower energy and a negative effect on vehicle parts.

This problem is solved using an antiknock additive to gasoline containing one or a mixture of alkoxy substituted benzene of the general formula (I),

where R is a radical With ₂ H ₅ About or CH ₃ About and additionally aniline in their mass ratio of 1: 1.

The technical result is achieved using an antiknock additive to gasoline containing one or a mixture of alkoxy substituted benzene of the general formula (I),

where R is a C ₂ H ₅ O or CH ₃ O radical and optionally aniline, in their mass ratio of 1: 1, the introduction of which into gasoline allows to achieve an increase in the octane number of gasolines at lower concentrations.

Examples confirming the effectiveness of alkoxysubstituted benzenes in combination with aniline were determined by the increase in the octane number determined by the motor method (ORM) and the research method (ORI) in the reference fuel mixture of isooctane and normal heptane (70:30 vol.%, Respectively).

Example 1

Phenetol (ethyl phenyl ether), taken in an amount of 5 wt.% In relation to the reference fuel mixture, gave an increase in HF by 2 units. (OFM) and 4 units. (OCHI).

Example 2

Anisole (methylphenyl ether), taken in an amount of 5 wt.% In relation to the reference fuel mixture, gave an increase of 1.5 units. (OFM) and 3.5 units. (OCHI).

Example 3

Aniline, taken 2.5 wt.% In relation to the reference fuel mixture, gave an increase of 7.5 units. (OFM) and 9.5 units. (OCHI).

Example 4

A mixture of phenethol and aniline in a ratio of 1: 1, respectively, taken in an amount of 5 wt.% In relation to the reference fuel mixture, gave an increase in HF by 10 units. (OFM) and 14 units. (OCHI).

Example 5

A mixture of anisole and aniline in a ratio of 1: 1, respectively, taken in an amount of 5 wt.% In relation to the reference fuel mixture, gave an increase of 9 units. (OFM) and 13.5 units. (OCHI).

Example 6

The additive, consisting of anisole and phenethol in a ratio of 1: 1, in a mixture with aniline in a ratio of 1: 1, taken in an amount of 5 wt.% Relative to the reference fuel mixture, gave an increase of 9.2 units. (OFM) and 14 units. (OCHI).

The combination of these components allows you to effectively raise the octane number of hydrocarbon fuels (fuels), and at the same time, the effect of synergism is manifested and their operational properties are preserved longer.

Similar results were obtained on samples of direct race gasolines from oil, gas stable gasoline (GHS), aviation gasoline, aviation kerosene, commercial gasoline grades AI 80, AI 92, AI 95, AI 98, with the highest efficiency obtained on the most low-octane samples.

Information sources

1. Fuels, lubricants, technical fluids. Assortment and application: Reference. I.G. Anisimov, K.M. Badyshtova, S.A. Bnatov et al.: Ed. V.M.Shkolnikov. Second edition, revised and supplemented. - M .: Publishing center "Tekhinform", 1999. - 596 p.: Ill.

2. Patent RU 2078118 class. С10L 1/18, 04/27/1997.

3. Patent US 4312636.

4. Patent US 4412847.

5. Patent RU 2153631.

6. A.M. Danilov. The use of additives in fuels. - M .: Mir Publishing House, 2005. - 288 p., Ill.

Claims (1)

A gasoline antiknock additive containing one or a mixture of alkoxy substituted benzenes of the general formula (1)

where R is a radical With ₂ H ₅ About or CH ₃ About and additionally aniline in their mass ratio of 1: 1.