WO2007067090A1 - Alkoxy-substituted anilines or the mixtures thereof in the form of additives used for increasing fuel-detonation resistance - Google Patents

Abstract

The invention relates to individual alkoxy-substituted anilines or to the mixtures thereof embodied in the form of components, additives and/or sinergents with or without oxygenates or in the form of mixtures thereof increasing the detonation resistance of hydrocarbon combustibles (fuels) and to fuel composition based thereon. Said fuel compositions (contents, formulations) are characterised in that alkoxy-substituted anilines with a mass ratios of 0-100 % or 0-1-25 % with respect to the hydrocarbon combustibles (fuels) are used (applied) in the form of components, additives and/or sinergents for increasing the octane number of hydrocarbon combustibles (fuels). The fuel compositions (contents, formulations) are characterised in that alkoxy-substituted anilines containing oxygenates in a quantity of 0.1-90 mass % and oxygenates up to 100 %, respectively, and in a quantity of 0.1-40 mass % with respect to the hydrocarbon combustibles (fuels) are used in the form of components, additives and/or sinergents for increasing the octane number of hydrocarbon combustibles (fuels).

Description

 Individual alkoxylated anilines or their mixtures as components, additives (additives) or / and synergents without or with oxygenates, or mixtures thereof, effectively increase the resistance to detonation of hydrocarbon fuels (fuels) and fuel compositions based on them.

 Application area

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

 State of the art

 Individual alkoxylated anilines or their mixtures as components, additives (additives) or / and synergents without or with oxygenates, or mixtures thereof, effectively increase the resistance to detonation of hydrocarbon fuels (fuels) and fuel compositions based on them.

 It is known that direct race gasolines consist of stable hydrocarbons that can be stored in gas storages without noticeable gum formation [1, 4].

However, the use of gasoline in internal combustion engines causes the detonation which promotes its premature ^'wear, reduced power, increased fuel consumption and its incomplete combustion, which leads to the formation of carbon monoxide and hydrogen thus increasing the smoke [1,2,4] .

With the advent of internal combustion engines operating at high compression ratios, the problem of increasing the octane number of hydrocarbon combustibles (fuels) arose [1,2,4]. 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 [1-7].

 Since direct race gasolines, or refining gasolines, are highly enriched with normal paraffin hydrocarbons, their octane numbers usually do not exceed 60 units. [1-4].

 Currently, the demand for high-octane hydrocarbon fuels (fuels) has increased and continues to grow [1–8, 16.17].

 Thermal cracking made it possible to sharply increase gasoline production and improve its quality [1,4].

 The decrease in the tendencies of cracked gasolines to detonation is due to the admixture of olefin hydrocarbons formed during the thermal decomposition of large molecules [1-7].

 Continuous development and improvement of aviation and automotive technology requires the creation of new high-octane fuels [1-7].

 This problem can be solved by creating new chemical processes of reforming gasoline of direct race, catalytic cracking and catalytic reforming or by adding special antiknock additives and high-octane components to hydrocarbon fuels (fuels) [1,4]. In this case, a synergistic effect may occur [1-7].

Although it is considered to be promising to obtain high-octane hydrocarbon fuels (fuels, gasolines) by technological means, the development of the methods themselves and the more so the creation and construction of new technological units for producing high-octane fuels requires huge capital costs, which is not always acceptable for many countries. Therefore, the most technologically and economically advantageous is the use of antiknock additives to produce high-octane hydrocarbon combustibles (fuels, gasolines).

 It is known that to increase the octane number of fuels, both ash and ash-free antiknock additives (additives) are used (used) [1-17].

 Well-known, but currently little used ash antiknock additives (additives) are organic compounds of manganese, iron, copper, chromium, cobalt, nickel, rare earth elements, lead [1,4,5,17], etc.

 However, all of them are highly toxic, especially organic compounds of lead 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 pecypc [l, 4, 5, 10-17].

 Ashless antiknock additives (additives), although less effective than ash ones, are more widely used and used, especially in combination with other components [1-15,17].

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

So, the additive Extralin TU 6.02.571-90 is known, containing in percentage weight ratios dimethylaniline up to 4.5%, aniline up to 6% and N-methylaniline up to 100% [14]. 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 [14]

 The disadvantages of this type of additives are: their limitation in content due to the increase in oxidation products, tar formation in gasoline during storage, and carbon formation during operation in the engine at an increased concentration thereof, and a relatively low increase in octane number in fuels [14, 17].

 Homologues of benzene are also known as antiknock agents: xylene, ethylbenzene, toluene [14, 16, 17], which increase the octane number of fuels very slightly.

 It is known to use oxygenates and their mixtures of ethyl or methyl alcohol with higher molecular weight alcohols as antiknock agents: methyl tert-butyl ether and its mixture with isobutyl alcohol in ratios of 60–80% and 40–20%, respectively [14].

 The disadvantages of such additives (additives) is a slight increase in the octane number of gasolines with a high content of up to 25%.

To date, there is a very limited range of ashless antiknock additives (additives) in the form of individual compounds (substances), which does not allow creating new types of high-octane hydrocarbon fuels (fuels) based on them, with the required properties for each particular case, depending on the goals or universal properties. This result can be achieved if aromatic amines are used as components of hydrocarbon combustibles (fuels). It is well known that the properties of compounds (substances) depend mainly not only on the elements that make up their molecules, but also on the relative position of these elements or groups of atoms of the elements with respect to each other, and also due to which bonds their association in the molecule takes place substances, that is, the design of the 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 (soy units), which in turn can significantly affect the properties of the entire system as a whole.

 It is known that hydrocarbon fuels (fuels) consist of a mixture of various hydrocarbons, which, with a certain combination of components, can acquire the desired 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 [1-7].

 To regulate such processes is used

(accepted) such compounds (substances), the excitation of molecules of which can occur only from one particular factor (for example, an electric spark) and transfer the excitation is sensitized to the whole system and at the same time inhibit other factors that prematurely affect this process, for example, high temperature effects (thermal) impact on b

system, which is the determining condition for the optimal operation of internal combustion engines.

 Aromatic amines can, in combination with hydrocarbon fuels (fuels), consisting of a mixture of various hydrocarbons, form intermolecular bonds with the molecules of the substances in the composition of the fuels through the formation of complexes, with charge transfer, π - complexes, σ - complexes, as well as free stable radicals and other active intermediate products with resonant energy exchange or new formations [18-32], 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 just one single factor, for example, from an electric discharge, which is very important when certain processes occur under these conditions.

 The use of anisidines (methoxyanilines, aminoanisoles) for the preparation of pharmaceuticals is known. preparations - derivatives of guaiacol and others, and for the synthesis of azo dyes [33].

 The use of phenetidines (ethoxyanilines, aminophenetols) for the preparation of drugs and for the synthesis of dyes (eg triarylmethane) is known [34].

For the first time, in order to increase the octane number of hydrocarbon combustibles (fuels), we theoretically determined and practically confirmed the possibility of using (using) aromatic compounds (substances) in the structure of molecules of which amino and alkoxy groups are combined that are in the ortho, meta, para position relative to each other. In this case, prototypes can be selected as osigenates: ethyl or methyl tert-butyl ether, and aniline, xylidine, toluidine, which are primary amines.

 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, the energy of fuels and the negative effect on the rubber parts of cars are reduced [14, 16.17].

 The disadvantages of additives containing aniline and its derivatives are their instability, increased gumming due to which their permissible concentrations are limited to 1-1.3% (mass), the need for their use in combination with antioxidants.

 Disclosure of the invention.

 This problem is solved by using (using) alkoxy-substituted individual anilines or their mixtures as components, additives (additives), and / or synergents without, or in combination with oxygenates, which increase the resistance to detonation of hydrocarbon fuels (fuels).

 The effectiveness of alkoxy substituted anilines was 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).

 The best examples of the invention.

Example 1. Para-ethoxyaniline, taken 1.3% of the mass, in relation to the reference fuel mixture gave an increase in HF by 5.5 units. (OFM) and 7 units. (OCHI).

Example 2. Ortho-ethoxyaniline, taken 1.3% of the mass, in relation to the reference fuel mixture gave an increase in NF by 4 units. (OFM) and 6 units. (OCHI) Example Z. Meta-ethoxyaniline, taken 1.3% of the mass, in relation to the reference fuel mixture gave an increase in HF by 3.8 units. (OFM) and 5.6 units. (OCHI).

 Example 4. Para-methoxyaniline, taken 1% of the mass, in relation to the reference fuel mixture gave an increase in HF by 2.5 units. (OFM) and 5 units.

(OCHI).

 Example 5. Ortho-methoxyaniline, taken 1.3% of the mass, in relation to the reference fuel mixture gave an increase in HF by 3.1 units. (OFM) and 5 units.

(OCHI)

Example b. Meta-methoxyaniline, taken 1.3% of the mass relative to the reference fuel mixture gave an increase in HF by 2 units. (OFM) and 4.2 units.

(OCHI).

 Example 7. A mixture of para-ethoxyaniline and ortho-ethoxyaniline in a ratio of 1: 1, taken 1.3% of the mass, in relation to the reference fuel mixture gave an increase in HF by 5.5 units. (OFM) and 7.5 units. (OCHI).

Example 8. A mixture of para-ethoxyaniline and MTBE in a ratio of 1: 1, taken 3% of the mass, in relation to the reference fuel mixture gave an increase in HF by 7 units. (OFM) and 9.5 units. (OCHI).

 Example 9. A mixture of para-methoxyaniline and methyl tert.-butyl ether (MBE) in a ratio of 1: 1, respectively, taken 3% with respect to the reference fuel mixture gave an increase in HF by 6 units.

(OFM) and 9 units. (OCHI).

 Example 10. A mixture of para-ethoxyaniline and isopropyl alcohol

(IPS) in a ratio of 1: 5, respectively, taken 10% of the mass relative to the reference fuel mixture gave an increase in HF by 10 units

(OFM) and 14 units. (OCHI).

 Example 8. A mixture of ortho-methoxyaniline and isopropyl alcohol

(IPS) in a ratio of 1: 5, respectively, taken 10% of the mass relative to the fuel mixture gave an increase of 9 units. (OFM) and

12 _{5 5} units (OCHI).

 Example 9. Papa-ethoxyaniline, taken 1.3% of the mass, in relation to gasoline direct race 58 units. HFM, gave an increase in HF by 14 units. (OFM) and 17.5 units. (OCHI).

 Industrial applicability.

Similar results were obtained on samples of gasoline direct race from oil 58 units. (OFM), gas stable gasoline (GHS) 66.5 units. (ОЧМ), aviation gasoline, aviation kerosene, commercial gasoline AI 80, AI 92, AI 95, AI 98.

Sources of information taken into account.

 1. Fuels, lubricants, technical fluids. Assortment and application: Reference book / I.G. Anisimov, K.M. Badyshtova, CA. Bnatov et al .: Ed. V. M. Shkolnikova. Second edition, revised and enlarged. - Moscow .: Publishing center "Texinform", 1999.-596 with: ill.

 2. B.A. Pavlov and A.P. Terentyev. Organic chemistry course. - Moscow .: State Scientific and Technical Publishing House of Chemical Literature, 1961. - 592 p.

3. E. S. Khotinsky. Organic chemistry course. - Kharkov.:

Publishing House of the Kharkov Order of the Red Banner of Labor

State University named after A. M. Gorky, 1959.- 724 p.

 4. E.G. Rozantsev. Destruction and stabilization of organic materials. - Moscow .: 3nanie Publishing House, 1974.-64 p.

5. A.E. Chichibabin. The main principles of organic chemistry. Volume I. -

Moscow: State Scientific and Technical Publishing House of Chemical Literature, 1963. - 912 p.

 6. N.L. Glinka. General chemistry. Twelfth Edition. - Moscow,

Leningrad .: Publishing house "Chemistry", 1965. - 688 p.

7. B. H. Stepanenko. Organic Chemistry Course Part I.

Aliphatic compounds. - Moscow .: Publishing house "Higher school", 1976. - 448 p.

 8. G.I. Shor, V.A. Vinokurov, I.A. Golubeva. Production and application of additives to petroleum products in the new business environment. Ed. I. G. Fuchs. - Moscow .: Oil and Gas Publishing House, 1996.- 44 p.

 9. A.S. USSR 152526, cl. C lO L 1/18; C 10L 1/26 1963,

Y. Patent of the Russian Federation 2032708, cl. C lO L 1/18 .. 1995 l l. K.K. Panok, I.A. Ragozin. Dictionary of Fuels, Oils, Lubricants, Additives and Special Liquids.- Moscow, ed

“Chemistry”, 1975. - 326 p.

 12. Patent of the Russian Federation 2064965, cl. C lO L 1/18, 1996,

lZ. Patent of the USSR 461512 class. C 10 L 1/18, 1975.

 14.Patent of the Russian Federation 2078118 to l. C 10 L 1/18, 1997,

 15.Patent RF 2184767 class. C 10 L 1/18, 2002.

 16. S. H. Onoychenko. The use of oxygenates in the production of promising automotive gasolines. - Moscow, Tekhnika LLC Tyma Group. 2003 .-- 64 p.

 17.A. M. Danilov. The use of additives in fuels. - Moscow .:

Publishing house "Mir", 2005. -288s, ill.

 18.A.H. Nesmeyanov, N.A. Nesmeyanov. The beginning of organic chemistry.

The first book .- Moscow .: Publishing house "Chemistry", 1974.-624c.

19.A.H. Nesmeyanov, N.A. Nesmeyanov. The beginning of organic chemistry.

The second book .- Moscow .: Publishing house "Chemistry", 1974. -744с.

 20. J. Roberta, M. Caserio. The basis of organic chemistry. Volume 1. -

Moscow .: Publishing house "Mir", 1978. - 848 p.

 21.J Roberta, M. Caserio. The basis of organic chemistry. Volume 2. - Moscow .: Publishing house "Mir", 1978. - 888 p.

 22. F. Kern, P. Sandberg. Advanced course in organic chemistry.

Book 1. structure and mechanisms. - Moscow .: Publishing house "Chemistry",

1981. 52 Oc.

 23. J. March. Organic chemistry. Reactions, mechanisms and structure. Volume 1. - Moscow .: Publishing house "Mir", 1987.- 384s.

 24. J. March. Organic chemistry. Reactions, mechanisms and structure.

Volume 3. - Moscow .: Publishing house "Mir", 1987.- 464s.

 25.K. Ingold. Theoretical Foundations of Organic Chemistry. - Moscow .:

Publishing house "Mir", 1973. - 1056с. 26. J. Mathieu, P. Panico. The course of theoretical foundations of organic chemistry. - Moscow .: Publishing house "Mir", 1975. - 556s. 27. Izv. USSR Academy of Sciences. Ser. Chem., 1978. N "9 ₅ with 2134-2136.

28. Izv. USSR Academy of Sciences. Ser. Chem., 1980. Xs2, pp. 421-424.

29. Izv. USSR Academy of Sciences. Ser. Chem., 1980. N ° 4, s 942-943.

 Z. Izv. USSR Academy of Sciences. Ser. Chem., 1981. Jfe9, from 2008-2014.

 Z l. USSR Academy of Sciences. Ser. Chem., 1993. JY27, since 1321.

 32. Coordination Chemistry, 1994, Volume 20, Ns4, p. 311-317.

 33. Brief chemical encyclopedia. Ed. count I. L. Knunyants (ed.) And others, t. 1, M., “Soviet Encyclopedia)), 1961. t.

(Encyclopedias. Dictionaries. Directories), vol. 1. A-E. 1961., 1262 stb. with ill.

 34. Brief chemical encyclopedia. Ed. count I. L. Knunyants (ed.) And others, vol. 5, M., “Soviet Encyclopedia)), 1967. vol. (Encyclopedias. Dictionaries. Directories). T. 5. TI. 1967., 1184 stb. with ill.

Claims

CLAIM. 1. Alkoxy-substituted anilines of the general formula (I) are individual or mixtures thereof as components, additives (additives) and / or synergents without or with oxygenates or mixtures thereof, which effectively increase the detonation resistance of hydrocarbon fuels (fuels) and fuel compositions based on them.

(I) when R = - OC2H5 in the ortho- or meta- or para-position means a compound of ortho- or meta- or para-ethoxyaniline, respectively synonyms: ortho- or meta-, or para-phenethidine  ortho- or meta- or para-aminophenetole when R = -, the NCH in the ortho- or meta- or para-position means a compound of ortho- or meta- or para-methoxyaniline, respectively synonyms: ortho- or meta-, or para-anisidine  ortho- or meta- or para-aminoanisole  2. Fuel compositions (compositions, formulations), characterized in that, as components, additives (additives), and / or synergents to increase the octane number of hydrocarbon fuels (fuels), individual alkoxylated anilines or mixtures thereof according to claim 1 are used (used) . taken in mass ratios of 0-100% and 0.1-25% in relation to hydrocarbon fuels (fuels). 3. Fuel compositions (compositions, formulations), characterized in that as components, additives (additives), and / or synergents to increase the octane number of hydrocarbon of fuels (fuels), alkoxy substituted anilines are used (used) according to claim 1 and claim 2, taken with oxygenates in mass ratios of 0.1-90% and oxygenates up to 100%, respectively, and O ₃ 1-40% with respect to hydrocarbon fuels ( fuels).