EA000882B1 - Multi-functional additive to gasolines and motor fuel for internal combustion engines - Google Patents

Abstract

1. A multi-functional additive to gasolines based on ethyl alcohol, containing N-methylanine, characterized in that further containing amide-based cleansing admixture and a stabilizer having the following component ratio, wt. %: N-methylanine 6,0-12,0 Stabilizer 0,2-20,0 Amide-based cleansing admixture 0,5-1,5 Ethyl alcohol remaining to 100,0 2. An additive of claim 1, characterized in that aliphatic alcohols C3-C5 or mixtures therof. 3. An additive of claims 1 and 2, characterized in that the cleansing admixture represents a mixture of amide-product of polyamide condensation of general formula NH2-(CH2)2-(NH-CH2)n-NH2, wher n is 0-4 with C7-C20 fatty carboxylic acids(5-10 % by weight); aliphatic alcohols C3-C4 (25-40 % by weight); C8-C10-monoalkylphenyl esterof polyethyleneglycol having 4 to 7 oxyethylated groups (0,35-5,0 % by weight) and hydrocarbon fraction with a boiling range between 180 degree C-350 degree C. 4. An additive of claims 1 t o3, characterized in that further contains from 0,2 to 0,4 % by weight of anticorrosion component. 5. An additive of claim 4, characterized in that the anticorrosion component is selected from the group containing: fatty amines of general formula RNH2, where R is C12-C18; or quarternary ammonium salts of higher carboxylic or alkoxyaromatic acids having C12-C18 carbon atoms and polyethylene-(or polypropylene)-polyamines having from 2 to 8 amino groups; or amides and imidazolines produced on the base of condensation of higher carboxylic or alkyloxyaromatic acids having C12-C18 carbon atoms with polyethylene-(or polypropylene)-polyamine having from 2 to 8 amino groups; or succinimides based on alkenylsuccinic anhydrate having C12-C30 carbon atoms and fatty amines of general formula RNH2 (R is C12-C18), or polyethylene-(polypropylene)-polyamines having from 2 to 8 amino groups; or a mixture of above-said products. 6. An additive of claims 1 to-5, characterized in that further contains from 0,01 to 0,1 % by weight of antioxydant. 7. An additive of claims 1 to 6, characterized in that the antioxydant is selected from a group containing: 2,6-di-tert- butyl-4-methylphenol or a solution of mixture of shielded phenols in toluene. 8. An additive of claims 1 to 7, characterized in that further contains an organic fat-soluble coloring agent. 9. Motor fuel for internal combustion engines based on gasoline and multi-functional additive of claims 1 to 8, characterized in that contains an additive as a multi-functional additive amounting from 2 to 15 % by weight.

Description

The present invention relates to the refining and petrochemical industry, in particular, to a multifunctional additive to gasoline, as well as fuel containing this additive, intended for use in internal combustion engines.

Know the use of octane (anti-knock) additives based on aromatic amines: N-methylaniline, ptoluidin, xylidines, etc. (M.O. Lerner "Chemical controllers for the combustion of motor fuels", M., Chemistry, 1979, pp. 84-89). Anti-knock additive based on aromatic amines (ADA) allows to obtain an increase in the octane number of up to 5.5 units at a concentration in gasoline of not more than 1.3 wt.%.

Further increase in its concentration leads to a significant increase in the formation of resins, organic sediments and deposits in the fuel supply system. To eliminate this drawback, a detergent is added to the additive, as well as antioxidants.

The introduction of detergent additives due to the tightening of standards for toxic emissions of vehicles, and therefore the use of detergents in gasoline becomes mandatory.

Known multifunctional additive to motor gasoline based on N methylaniline, an organic derivative of manganese and detergent additives AUTOMATIC (Patent RF № 2114901, cl. C 10L 1/18, 1/22, 1998).

Increased wear of engine parts, reduced reliability of spark plugs and the high cost of methylcyclopentadienyl tricarbonyl manganese limit the use of this additive.

As the octane components of gasolines, oxygen-containing compounds are also widely known and widely used - oxygenates, which include low molecular weight alcohols, ethers, and mixtures thereof.

Gasoline-alcohol mixtures are homogeneous mixtures of lower aliphatic alcohols (ethanol, methanol) with gasoline, used as fuel in carburetor internal combustion engines, usually contain 3-15 wt.% Alcohol. Such mixtures have a high detonation resistance (the addition of 10% by weight of methanol increases the octane number by 4-6 units, thereby increasing engine power by 4-6%). In addition, the use of gasoline-alcohol mixtures reduces the concentration of nitrogen oxides and unburned hydrocarbons (CH) in the exhaust gases (OT).

Known octane additive to gasoline, which is a mixture of ethyl alcohol and methyl tert-butyl ether (MTBE) (US Patent No. 4,207,077, c. C 10L 001/18, 1980).

Known octane additive to gasoline containing waste hydrolysis production of ethyl alcohol from wood raw material (8-80 wt.%), Ethyl alcohol (the rest is up to 100 wt.%) And the fuel composition based on gasoline, containing the specified additive in the amount of 2-20 wt. .% (RF Patent No. 2068871, Cl. C 10L 1/02, 1/18, 1996). The disadvantage of this invention is the lack of co-solvent based on these wastes and their lack of effectiveness in stabilizing the gasoline-alcohol mixture, which requires the use of them in a significant concentration (more than 8 wt.%).

The main disadvantage of oxygenates is their lower calorific value than gasoline (for example, with the introduction of 15 wt.% Methanol or ethanol, it decreases by 8 and 7%, respectively) and the need to use them in high concentrations, which leads to higher prices for gasoline.

Known motor fuel containing oxygenate, of the following composition, wt.%: Gasoline - 70-90; ethyl alcohol - 5-20; MTBE - 4-12 (US Patent No. 4,207,077, cl. C 10L 001/18, 1980).

Known fuel composition containing gasoline with the addition of the antioxidant phenylenediamine and octane additives based on ethyl alcohol, ethyl tert-butyl ether (ETBE), tert-butyl alcohol (TBS) (US Patent No. 4,207,076, class C 10L 001/18, 1980).

Known motor fuel based on gasoline, containing a mixture of ethyl alcohol - 1 -1 2 wt.% And Isobutanol - 2-4 wt.% As octane additives (US Patent No. 4,541,836, class C. 10L 001/18, 1985).

A significant disadvantage of gasoline alcohol mixtures is their toxicity, poor starting properties (due to low saturated vapor pressure), phase instability, i.e., separation at negative temperatures and in the presence of water, the possibility of deterioration of the corrosive properties of the base gasoline after it is mixed with watered ethanol .

The increase in the corrosivity of gasoline-alcohol mixtures (especially during long-term storage of flax) is due to the accumulation of acidic products that are formed as a result of oxidative processes initiated by oxygenates. In order to eliminate these drawbacks, it is necessary to introduce stabilizers in order to prevent the gasoline-alcohol mixture from splitting with decreasing temperature and the anticorrosive component in order to provide protection against corrosion.

Compositional additives to fuels with enhanced anti-knock and environmental properties, obtained by combining various nitrogen, oxygen, and organometallic compounds with the addition of detergents, are known in the art.

For example, the known multifunctional additive for the production of motor gasolines based on N-methylaniline, containing ferrocene, aliphatic alcohols, Automag additive, antioxidant and aniline (RF Patent No. 2132359, cl. С 10L 1/18, 1/22, 1999).

The disadvantage of this invention is the presence of the organometallic component of ferrocene, which increases the wear of engine parts, increases gum formation and has a negative effect on the operation of catalytic converters in automobiles.

Also known additive to gasoline based on stabilized ethanol containing N-methylaniline, ferrocene and / or α-hydroxyisopropyl-ferrocene (RF Patent No. 2129141, cl. C 10L 1/18, 1999).

The disadvantages of the additive described in this patent are also the presence of ferrocene and / or its derivative, which increase the wear of engine parts, increase gum formation and have a negative effect on the operation of catalytic converters in automobiles.

From this patent is also known fuel composition containing this additive in the amount of 1.5-5.0 wt.%. The disadvantages described above of oxygenate-containing fuel compositions also apply to the fuel composition presented in this patent.

The aim of the present invention is to eliminate the above disadvantages of an additive to gasolines by creating an ash-free multi-functional additive to motor gasolines based on ethanol, combining high anti-knock, anti-corrosion and detergent properties to ensure improved environmental and operational properties of fuel using commercial and fuel-approved components. and fuel containing it.

Ethanol is a renewable energy source and, given the growth trend of its use in the production of unleaded gasoline, the use of ethanol as an octane additive is promising.

To solve this problem, a multifunctional additive to gasolines based on ethyl alcohol containing Nmethylaniline is proposed, characterized in that it additionally contains an amide-based detergent additive and a stabilizer in the following ratio, wt.%:

N-methylaniline 6.0-12.0

Stabilizer 0.2-20.0

Amide-based detergent 0.5-1.5

Ethyl alcohol Else to 100.0

Introduction to the composition of the additive as a stabilizer alcohol composition of C ₃ -C ₅ in the established ratio lowers the cloud point of the gasoline-alcohol mixture to ensure its phase stability.

As a detergent additive in the proposed composition, an amide mixture is used - a condensation product of a polyamine of the general formula NH2- (CH2) 2- (NH-CH2-CH2) _n -NH2, where n = 0-4 with C20-fatty carboxylic acids (5- 10 wt.%); C ₃ -C ₄ aliphatic alcohol (25-40 wt.%), polyethylene glycol C ^ C ^ monoalkylphenyl ether with 4–7 oxyethylene groups (0.3–5.0 wt.%) and a hydrocarbon fraction with a boiling point of 180- 350 ° C. This additive has detergent and anti-corrosion properties and provides a reduction in the content of toxic emissions: carbon monoxide (CO) and unburned hydrocarbons (CH) in the exhaust gases (exhaust gases) of motor vehicles.

The additive may additionally contain from 0.2 to 0.4 wt.% Anti-corrosion component.

To enhance the effectiveness of the detergent and anti-corrosion effect of the additive, the anti-corrosion component is selected from the group consisting of:

- fatty amines of the general formula RNH ₂ , where R = C _J2 -Ci ₈ ; or

- Quaternary ammonium salts of higher carboxylic or alkyloxyaromatic acids with the number of carbon atoms Q ₂ -C ₁₈ and polyethylene (or polypropylene) polyamines with the number of amino groups from 2 to 8; or

- amides and imidazolines obtained on the basis of condensation of higher carboxylic or alkyloxyaromatic acids with the number of carbon atoms C ₁₂ -C ₁₈ with polyethylene (or polypropylene) polyamines with the number of amino groups from 2 to 8; or

- succinimides based on alkenylsuccinic anhydride with the number of carbon atoms from 1 2 to 30 and fatty amines of the general formula RNH ₂ (R = C ₁₂ -C ₁₈ ), or polyethylene (polypropylene) polyamines with the number of amino groups from 2 to 8; or

- a mixture of the above products.

The additive may also optionally contain from 0.01 to 0.1 wt.% Antioxidant.

The antioxidant for the proposed additive is selected from the group including:

2,6-di-tert-butyl-4-methylphenol or a solution of a mixture of screened phenols in toluene, commercially available under the trade names Agidol-1 or Agidol-12, respectively.

In order to label a fuel modified with this additive to give it a characteristic color from blue to blue-green, the multifunctional additive may contain an organic, fat-soluble dye.

High anti-knock efficiency when using the proposed multifunctional additive is provided by using a synergistic mixture of ethyl alcohol and N-methylaniline in its composition in a selected ratio.

The combination in the composition of the additives of the above components is new and allows you to get an ashless multi-functional additive with anti-corrosion and detergent properties, higher in comparison with the known additives anti-knock efficiency and physical stability.

It is also proposed fuel for internal combustion engines based on gasoline, containing a multifunctional additive of the above composition, in the amount of 2-15 wt.%. The fuel containing this additive has improved environmental and operational properties, as described above.

Multifunctional additive according to this invention is prepared by waste-free technology using standard equipment by mixing the components to obtain a homogeneous solution.

All components used in the composition of the additive are products of industrial production and are manufactured according to the appropriate specifications and state standards.

To illustrate the proposed technical solution, 4 samples of the additive of different composition were prepared, which in an amount of from 2 to 15 wt.% Were introduced into the fuel composition. As the base of the fuel composition, gasoline with an octane rating of 91.2 units was investigated using the research method.

The composition of the samples of multifunctional additives and their functional properties are given in table. 1, and the test results of the fuel composition in table. 2

To assess the washing efficiency of the multifunctional additive, bench tests of the additive samples were carried out on a single-cylinder IT installation using qualification assessment methods. Washing efficiency is determined by the coefficient of flushing (K _see ) and the coefficient of prevention (K _etc. ). The higher the indicated factors, the more effective the additive.

The evaluation of the anticorrosion properties of the additive samples was carried out by an electrochemical method by measuring the current of electrochemical corrosion after 1 h of testing, and the lower the current value, the more effective the additive.

The test of low-temperature properties of samples of multi-functional additives carried out according to GOST 5066-56.

The increase in the octane number of the additive samples is determined on the unit UIT-86 according to GOST 511-82 by the motor method. The detonation resistance of samples of fuel compositions containing an additive is determined according to GOST 8226-82 by a research method.

Table 1

The composition of the samples of the proposed multi-functional additives and their functional properties

Nn number Name of components and indicators The content of components in the samples, wt.% NTD Example 1 Example 2 Example 3 Example 4 I The composition of fuel additives one N-methylaniline 6 12 ten eight TU 2471-269-00204-16896 2 Alcohols C ₃ - C ₅ 0.5 five 2.5 20 GOST 9805 or GOST 9536 3 Detergent additive 0.5 1.5 1.0 1.0 TU 38.401-58-33-92 four Anticorrosive component 0.4 0.2 0.2 0.2 MRTU 6-02-740-79; TU 38.101146-76 and others. five Antioxidant - 0.1 0.05 - TU 38.302-16-371 6 Ethanol The rest is up to 100 TU 38.402-62-117-98 II Functional properties one Anticorrosion efficiency: electrochemical corrosion current, μα at a concentration of 0.5 wt.% In toluene 17 eight 20 21 2 Washing efficiency: Kcm.,% CRC 78.6 4.9 91.6 9.1 84.7 7.5 83.9 6.2 3 Anti-knock properties in a mixture of 70% isooctane and 30% n-heptane at a concentration of 5.0 wt.% 3.8 4.5 4.2 4.0

four Cloud point in a mixture of 70% isooctane and 30% n-heptane at a concentration of 5.0% by weight, ° С Minus 18 Below minus 30 Minus 30 Below minus 35

table 2

The test results of fuel compositions containing the proposed multifunctional additive

Nn number Name of components and indicators The content of the additive (wt.%) And test results Example 1 Example 2 Example 3 Example 4 Example 5 Components one The additive according to example 2 2.0 2 The additive according to example 2 6.0 3 The additive according to example 3 5.5 four The additive according to example 4 6.0 five The additive according to example 4 15.0 Indicators one Research octane number 92.6 95.0 94.3 94.6 98.4 2 Cloud point, ° С Minus 31 Below minus 35 Minus 30 Below minus 40 Below minus 30 3 Washing properties: rinsing time, min 26 9 15 13 four

The introduction of the ashless multi-functional additive according to this invention will allow:

- to replace toxic ethyl liquid and other metal-containing anti-knock in order to increase the volume of unleaded gasoline;

- to increase the growth of the octane number, approved for use by domestic lead-free antiknocks;

- to improve the environmental and operational properties of gasoline by reducing the harmful emissions of lead oxide, CO and CH in the exhaust gases of automobiles, which will provide a solution to the important social problem of cleaning the air basin of large cities from harmful emissions during the operation of vehicles.

Claims (9)

1. A multifunctional ethanol-based gasoline additive containing Nmethylaniline, characterized in that it further comprises an amide-based detergent additive and a stabilizer in the following ratio, wt.%: N-methylaniline 6.0-12.0 Stabilizer 0.2-20.0 Amide based detergent 0.5-1.5 Ethyl alcohol Else up to 100.0 2. The additive according to claim 1, characterized in that C ₃ -C ₅ aliphatic alcohols or mixtures thereof are used as stabilizer. 3. The additive according to paragraphs. 1, 2, characterized in that the detergent additive is a mixture of an amide - a condensation product of a polyamine of the general formula N4 ^ (04 ₂ ) ₂ - (NH-CH ₂ -CH ₂ ) _n -NH ₂ , where n = 0-4 s С ₇ -C ₂₀ fatty carboxylic acids (5-10 wt.%); aliphatic alcohols C ₃ -C ₄ (25-40 wt.%); C ₈ -C _{! 0} -monoalkylphenyl ether of polyethylene glycol with 4-7 hydroxyethylated groups (0.3-5.0 wt.%) And a hydrocarbon fraction with a boiling range of 180 -350 ° С. 4. The additive according to claims 1 to 3, characterized in that it additionally contains from 0.2 to 0.4 wt.% Anti-corrosion component. 5. The additive according to claim 4, characterized in that the anti-corrosion component is selected from the group consisting of: - fatty amines of the general formula RNH ₂ , where R = C _J2 -Ci ₈ ; or - Quaternary ammonium salts of higher carboxylic or alkyloxyaromatic acids with the number of carbon atoms C ₁₂ -C ₁₈ and polyethylene (or polypropylene) polyamines with the number of amino groups from 2 to 8; or - amides and imidazolines obtained by condensation of higher carboxylic or alkyloxyaromatic acids with the number of carbon atoms C ₁₂ -C ₁₈ with polyethylene (or polypropylene) polyamines with the number of amino groups from 2 to 8; or - succinimides based on alkenyl succinic anhydride with the number of carbon atoms from 1 2 to 30 and fatty amines of the general formula RNH ₂ (R = C ₁₂ -C ₁₈ ), or polyethylene (polypropylene) polyamines with the number of amino groups from 2 to 8; or - a mixture of the above products. 6. The additive according to claims 1-5, characterized in that it further comprises from 0.01 to 0.1 wt.% Antioxidant. 7. The additive according to claim 6, characterized in that the antioxidant is selected from the group comprising 2,6-di-tert-butyl-4-methylphenol or a solution of a mixture of shielded phenols in toluene. 8. The additive according to claims 1 to 7, characterized in that it further comprises an organic fat-soluble dye. 9. Fuel for internal combustion engines based on gasoline and a multifunctional additive, characterized in that as a multifunctional additive it contains the additive according to claims 1-8 in an amount of from 2 to 15 wt.%.