RU2374303C1 - Fuel composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to oil refining and petrochemistry, specifically to a fuel composition designed for internal combustion engines. A hydrocarbon-based fuel composition for internal combustion engines is proposed, which contains an aromatic amine and is distinguished by that it also contains a multifunctional additive, which is a mixture of polyisobutylene-monoamine, polyester and corrosion inhibitor, polyethylenepolyamine of general formula H₂N-(CH₂-CH₂-NH-)_nH, where n=1-5, and a solvent, with the following ratio of components, wt %: aromatic amine 0.6 to 1.6; multifunctional additive 0.03 to 0.07; polyethylenepolyamine 0.0001 to 0.004; solvent 0.2 to 0.7; hydrocarbon base up to 100. The solvent is selected from: 2-ethylhexanol, toluene, xylene. The hydrocarbon base used in the fuel composition is a mixture of hydrocarbon fractions which boil at temperature between 25 and 220°C. The proposed fuel composition has good anti-detonation, detergent and anticorrosion properties and is made from industrially produced products.

EFFECT: use of the invention allows for obtaining high quality motor fuel: AI-92 (Regular-92), AI-95 (Premium-95), AI-98 (Super Euro-98).

3 cl, 5 tbl

Description

The invention relates to oil refining and petrochemicals, specifically to a fuel composition intended for internal combustion engines.

Known fuel composition for internal combustion engines, which contains 2-54% wt. benzene raffinate or benzene-toluene raffinate, 15-30% wt. toluene, 1-15% wt. a wide fraction of light hydrocarbons NK-70 ° C, 1-15% isopentane, 0.3-1.3% wt. monomethylaniline and up to 100% catalytic reforming gasoline. (Pat. RF №2198202, 2003).

A disadvantage of the known composition is the use in high concentrations of components containing aromatic hydrocarbons, the concentration of which in modern gasolines is limited.

Also known is a fuel composition for internal combustion engines, which includes 1-7% wt. hydrostabilized gasoline pyrolysis, 26-45% wt. gasoline catalytic cracking and / or gasoline direct distillation, 4-7% wt. pentane-amylene fraction, 0.3-1.3% wt. monomethylaniline, 0.3-3.0% wt. methyl tert-butyl ether or its mixture with tert-butyl alcohol, up to 20% wt. toluene and / or xylene, up to 5.5% wt. gasoline delayed coking, the rest is catalytic reforming gasoline. (Pat. RF №2203310, 2003).

The disadvantage of the described composition is the use in high concentrations of components containing aromatic hydrocarbons, and the presence of unstable components of catalytic and thermal processes, which creates problems with the implementation of restrictions on the content in modern gasolines of sulfur and, in combination with monomethylaniline, leads to increased deposits on the elements of the intake system.

Closest to the claimed is a fuel composition for internal combustion engines, which contains 1-10% wt. ethyl alcohol, 1-5% wt. fusel oil, 0.3-1.5% wt. additives based on aromatic amine, 0.001-0.1% wt. mixtures of propoxylated light neutralized distillate and naphthalene alcohol or a reaction product of higher carboxylic acids With ₁₀ -C ₃₀ polyalkanolamines or their alkyl derivatives and up to 100% wt. hydrocarbon base. The fuel composition as a hydrocarbon base contains a mixture of hydrocarbon fractions boiling in the temperature range 25-220 ° C, and as an aromatic amine - monomethylaniline or an ADA additive. (Pat. RF №2230775, 2004).

The disadvantage of this fuel composition is the presence of ethanol (usually watered) in it, which, when added to gasoline, can lead to phase instability, that is, delamination at low temperatures. The addition of alcohol also leads to an increase in the corrosiveness of gas-alcohol mixtures with respect to metals. Increased aggressiveness and a tendency to form deposits on engine elements is manifested especially with the simultaneous presence of ethanol and monomethylaniline in the fuel composition.

The objective of the invention is to develop a fuel composition based on industrial products with high anti-knock, detergent and anti-corrosion properties.

To solve this problem, a fuel composition for hydrocarbon-based internal combustion engines, including aromatic amine, is proposed. The fuel composition is characterized in that it further comprises a multifunctional additive, which is a mixture of polyisobutylene-monoamine, a polyester and a corrosion inhibitor, polyethylene polyamines of the general formula H ₂ N- (CH ₂ -CH ₂ -NH-) _n H, where n = 1-5, and solvent in the following ratio, wt.%:

Aromatic amine 0.6-1.6 Multifunctional additive 0.03-0.07 Polyethylene polyamines 0.0001-0.004 Solvent 0.2-0.7 Hydrocarbon base up to 100

Moreover, the solvent is selected from the group of 2-ethylhexanol, toluene, xylene.

As a hydrocarbon base, the fuel composition contains a mixture of hydrocarbon fractions boiling in the temperature range 25-220 ° C.

The proposed fuel composition is prepared by introducing the components into the hydrocarbon base with stirring.

To prepare samples of the fuel composition, the following components were used, which are industrial products.

Technical monomethylaniline according to TU 2471-248-05800142-2005 or an additive based on it, for example, ADA-SUPER according to STO 11605031-011-2007, is used as an aromatic amine in the fuel composition.

As a multifunctional additive, Keropur 3458 N, manufactured by BASF, is used, which is a mixture of polyisobutylene-monoamine, polyester, and a corrosion inhibitor.

It is a clear, yellowish, viscous liquid with the following characteristics:

density at 15 ° C, about 0.88 g / cm ³ ;

viscosity at 20 ° C, about 70 mm ² / s;

flash point over 55 ° C.

It gives a clear solution in organic solvents and is practically insoluble in water.

In the fuel composition using polyethylene polyamines of the General formula H ₂ N- (CH ₂ -CH ₂ -NH-) _n H, where n = 1-5, mol. mass = 60-230, density d = 0.95-l, 05 g / cm ³ according to TU 2413-357-00203447-99.

The solvent used is 2-ethylhexanol according to GOST 26624-85 or petroleum toluene according to GOST 14710-78, or xylene of oil grade A according to GOST 9410-78, etc.

As the hydrocarbon base, a mixture of hydrocarbon fractions boiling in the temperature range of 25-220 ° C, containing in wt.%: Stable catalytic cracking gasoline 10-80; raffinate 1-6; stable isomerizate 1-25; alkylate 1-20, methyl tert-butyl ether up to 15; stable reforming catalysis - up to 100.

When preparing samples of the proposed fuel composition as a hydrocarbon base used,% wt .:

Sample 1

stable catalytic cracking gasoline - 80;

raffinate - 6;

stable isomerizate 1;

alkylate - 1;

methyl tert-butyl ether - 1;

stable reforming catalysis - up to 100.

Sample 2

stable catalytic cracking gasoline - 30;

raffinate - 1;

stable isomerizate 23;

alkylate - 4;

methyl tert-butyl ether - 7;

stable reforming catalysis - up to 100.

Sample 3

stable catalytic cracking gasoline - 10;

raffinate - 1;

stable isomerizate 18;

alkylate - 14;

methyl tert-butyl ether - 15;

stable reforming catalysis - up to 100.

To illustrate the essence of the invention, 3 samples of the proposed fuel composition were prepared, the composition of which is shown in table 1.

Table 2 shows the results of comparative bench tests of fuel compositions on a VAZ engine (STO ANN 40488460-001-2004 technique).

From the data presented in table 2, it follows that the proposed compositions of the fuel compositions provide a low level of tendency of gasolines to form deposits and exceed this indicator in comparison with the prototype by ~ 6-10 times.

Similar data were obtained when other solvents — toluene or xylene — were used in fuel compositions.

Physico-chemical characteristics and test results of the prepared samples of the fuel composition are given in tables 3-5.

It should be noted that the bulk of gasoline is produced in the Russian Federation in accordance with GOST R 51105-97, the use of which ensures the reliable operation of cars with emission standards of Euro-2. Fuel compositions - sample 1 and sample 2 - were tested for compliance with the standards of this standard (tables 3 and 4). The test results showed compliance of the fuel composition - sample 1 - with the AI-92 gasoline standards (Regular-92), and the fuel composition - sample 2 - with the AI-95 gasoline standards (Premium-95).

In recent years, the share of modern imported cars meeting the requirements of Euro-3, Euro-4 has been growing in the country's car park. The operation of modern foreign cars requires the use of appropriate fuels. In 2005, VNIINP developed technical specifications TU 38.401-58-350-2005 for gasoline for Euro-4 cars. The fuel composition - sample 3 - was tested for compliance with the standards of this standard (table 5) and showed full compliance with unleaded gasoline AI-98 (SuperEuro-98).

Thus, the proposed fuel composition has high antiknock, detergent and anticorrosive properties and is prepared on the basis of industrial products. Using the invention will allow to obtain high-quality fuels for automobile brands: AI-92 (Regular-92), AI-95 (Premium-95), AI-98 (SuperEuro-98).

Table 1 The composition of the samples of the proposed fuel composition No. p / p Name of components The content of components,% wt. Sample 1 Sample 2 Sample 3 one monomethylaniline 1,6 1,0 - ADA Super - - 0.6 2 Keropur 3458 N 0,07 0.06 0,03 3 polyethylene polyamines 0.004 0.001 0.0001 four 2-ethylhexanol 0.2 0.4 0.7 5 hydrocarbon base up to 100 up to 100 up to 100

table 2 The results of comparative bench tests of fuel compositions on a VAZ engine (STO ANN 40488460-001-2004 technique) The formation of deposits on the engine of the VAZ Hydrocarbon base Fuel composition Prototype Pat. RF №2230775
AI-92 fuel with additives (alcohol content 10% wt., MMA 1.3% wt.) Sample 1 Sample 2 Sample 3 Sample 1 Sample 2 Sample 3 The formation of deposits on the engine of the VAZ 43 52 45 fifteen 13 10 97

Table 3 Test results of fuel composition No. 1 for compliance with Regular-92 gasoline standards in accordance with GOST R51105-97 class 2 No. p / p The name of indicators Norm actually Test method one Octane number, not less by research method 92.0 92.6 GOST 511 by motor method 83.0 83.6 GOST 8226 2 Lead concentration, mg per 1 dm ^{3 of} gasoline, no more 5* from GOST 28828 3 Density at 15 ° С, kg / m ³ 725-780 740 GOST R 510693900 four Mass fraction of sulfur,%, no more 0.0150 * 0.0035 ASTM D2622 5 Induction period of gasoline, min, not less than 360 Over 360 GOST 4039 6 The concentration of resin washed with a solvent, mg per 100 cm ^{3 of} gasoline, not more than 5 1,5 GOST 1567 7 Corrosion on a copper plate (3 hours at 50 ° C), units on a scale Grade 1 Grade 1 GOST 6321 8 Appearance Transparent Transparent visually 9 Volume fraction of aromatic hydrocarbons,% 42 * 28 ASTM D1319 10 Volume fraction of benzene,%, no more 3.0 * 0.6 eleven Saturated vapor pressure (DNP), kPa 45-80 52 GOST 1756 12 Fractional composition: volume fraction of evaporated gasoline,%, at temperature: GOST 2177 70 ° C 15-45 23 100 ° C 40-70 52 180 ° C, not less 85 91 The end of the boil of gasoline, ° C, not higher 215 198 The remainder in the flask,% vol., No more 2 1,2 13 Evaporation Index (IPP) 1000 681 GOST R 51105 clause 7.4 * Additional regional requirements of Moscow (No. 952-ПП dated 12/28/2004)

Table 4 Test results of fuel composition No. 2 for compliance with Premium-95 gasoline standards according to GOST R51105-97 class 2 No. p / p The name of indicators Norm actually Test method one Octane number, not less by research method 95.0 95.4 GOST 511 by motor method 85.0 86.1 GOST 8226 2 Lead concentration, mg per 1 dm ^{3 of} gasoline, no more 5* from GOST 28828 3 Density at 15 ° С, kg / m ³ 725-780 735 GOST R 510693900 four Mass fraction of sulfur,%, no more 0.0150 * 0.0019 ASTM D2622 5 Induction period of gasoline, min, not less than 360 Over 360 GOST 4039 6 The concentration of resin washed with a solvent, mg per 100 cm ^{3 of} gasoline, not more than 5 1,6 GOST 1567 7 Corrosion on a copper plate (3 hours at 50 ° C), units on a scale Grade 1 Grade 1 GOST 6321 8 Appearance Transparent Transparent visually 9 Volume fraction of aromatic hydrocarbons,%, no more 42 * 27 ASTM D1319 10 Volume fraction of benzene,%, no more 3.0 * 0.7 eleven Saturated vapor pressure (DNP), kPa 45-80 57 GOST 1756 12 Fractional composition: volume fraction of evaporated gasoline,%, at temperature: GOST 2177 70 ° C 15-45 41 100 ° C 40-70 60 180 ° C, not less 85 95 The end of the boil of gasoline, ° C, not higher 215 197 The remainder in the flask,% vol., No more 2 1.3 13 Evaporation Index (IPP) 1000 857 GOST R 51105 clause 7.4 * Additional regional requirements of Moscow (No. 952-ПП dated 12/28/2004)

Table 5 The test results of the fuel composition No. 3 for compliance with the standards of unleaded gasoline SuperEuro-98 class B TU 38.401-58-350-2005 No. p / p Name of indicator Units measuring Values Norms for class B according to TU Actually Octane number: one - according to the research method No less than 98.0 98.8 - by motor method Not less than 88 89 2 Lead concentration mg / dm ³ No more than 5 from 3 Density at 15 ° C kg / m ³ 720-775 743 four Sulfur concentration mg / kg No more than 50 10 5 Oxidation resistance min Not less than 360 Over 360 6 Resin concentration, mg / 100 cm ³ No more than 5 1.4 washed with solvent mg per 100 cm ^{3 of} gasoline 7 Copper plate corrosion units Grade 1 Grade 1 (3 hours at 50 ° C) on a scale 8 Appearance Transparent and bright Transparent and bright 9 Volume fraction % hydrocarbons - olefin, No more than 18,0 2 - aromatic No more than 35.0 26 10 Volume fraction of benzene % No more than 1,0 0.7 eleven Mass fraction of oxygen % No more than 2.7 2.7 12 Volume fraction of oxygenates % No more - methanol 3 0 - ethanol 5 0 - isopropyl alcohol 10 0 - isobutyl alcohol 10 0 - tert-butyl alcohol 7 0 - esters (C ₅ and above) fifteen fifteen - other oxygenates 10 0 13 Saturated steam pressure kPa 45.0-70.0 56 fourteen Fractional composition: - Volume fraction of evaporated gasoline at temperature % - 70 ° C (I70) 22.0-48.0 thirty 100 ° C (I100) 46.0-71.0 49 150 ° C (I150) Not less than 75.0 89 90% is distilled at a temperature ° C No higher than 190 153 - end of boiling ° C No higher than 210 197 - residue in the flask,% (by volume), % No more than 2 1,2 fifteen The maximum steam plug index (IPP) IPP = 10DNP + 7 (I70) Not standardized 860

Claims (3)

1. A fuel composition for hydrocarbon-based internal combustion engines, including an aromatic amine, characterized in that it further comprises a multifunctional additive, which is a mixture of polyisobutylene-monoamine, polyester and corrosion inhibitor, polyethylene polyamines of the general formula H ₂ N- (CH ₂ -CH ₂ -NH-) _n H, where n = 1-5, and the solvent in the following ratio of components, wt.%:
Aromatic amine 0.6-1.6 Multifunctional additive 0.03-0.07 Polyethylene polyamines 0.0001-0.004 Solvent 0.2-0.7 Hydrocarbon base Up to 100 2. The fuel composition according to claim 1, characterized in that it contains a solvent selected from the group: 2-ethylhexanol, toluene, xylene. 3. The fuel composition according to claim 1, characterized in that as the hydrocarbon base it contains a mixture of hydrocarbon fractions boiling in the temperature range 25-220 ° C.