RU2400529C1 - Multi-functional additive to automobile petroleum, and fuel composition which contains it - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention refers to multi-functional additive to automobile petroleum, which contains the following, wt %: methyl tertiary butyl ether 20-40; detergent additive containing friction modifier (Hitech 6437) up to 10; colour stabiliser - diethylamine or triethylene tetramine 0.01-0.2; anti-knock additive on the basis of aromatic amines, which includes N-methylaniline as the main component, is the rest. Invention also refers to fuel composition for internal combustion engines. Automobile petroleum by using the proposed additive meets the general requirements of European Standards.

EFFECT: additive within the proposed range and ratio of components together with high anti-knock detergent and corrosion-protecting properties has colour stability after 1 year of storage.

2 cl, 4 tbl

Description

The invention relates to the field of oil refining and petrochemicals, specifically to the composition of a multifunctional additive to gasoline and to a fuel composition containing this additive.

Known for the widespread use in the composition of motor gasoline antiknock additives based on N-methylaniline (N-MA) (A. Danilov. The use of additives in fuels. Reference edition. M., Mir, 2005, p.20-30).

Also known is an additive to motor gasolines based on methyl tert-butyl ether (MTBE), N-MA, methanol and detergent additive (Avtomag) in the following ratio, wt.%: 6.5-70 N-MA; 0.5-5 N, N-dimethylaniline; 0.5-27 tertiary butyl alcohol; 0.5-30 methanol; detergent additives - not more than 6, MTBE up to 100.

The additive is introduced into gasoline in a concentration of up to 20% wt.

(Pat. RF №2139914, 1999).

The disadvantage of this additive is the high methanol content, which increases its toxicity and hygroscopicity, and also reduces the stability of gasolines during storage. Avtomag detergent additive is effective for obsolete carburetor engines and is practically unsuitable for modern engines with direct fuel injection due to the low efficiency in removing tar deposits on intake valves and injectors.

Closest to the claimed is an additive to motor gasolines containing, wt.%: 6.5-70 N-MA, 0.2-27 tertiary butyl alcohol, not more than 6.0 detergent additives, 0.1-25 esters of acetic acid and fusel oil and up to 100 MTBE. As a washing additive, an additive containing the condensation product of a polyamine of the general formula NH ₂ - (CH ₂ ) ₂ - (NH-CH ₂ -CH ₂ ) _n -NH ₂ , where n = 0-4, with C ₇ -C ₂₀ - fatty acids. The additive is intended for use in gasoline in a concentration of up to 20% wt.

(Pat. RF №2155793, 2000).

The disadvantage of the additive is the presence of a detergent with low thermal stability, which does not provide the possibility of its use in the operation of injection internal combustion engines.

A significant drawback of the additive is also the tendency to change color during storage from light yellow to dark brown (color according to ASTM D 1500 from 0.5 to 8.0), as well as to increase the amount of deposits on the intake valves, especially when using the additive in the composition of gasoline containing cracked products.

The objective of the invention is to develop a multifunctional additive to motor gasolines based on aromatic amine, which has color stability during storage and high anti-knock, washing and anti-corrosion properties, as well as a fuel composition comprising this additive.

To solve this problem, a multifunctional additive to motor gasoline is proposed, containing% wt .:

Methyl tert-butyl ether 20-40 Detergent additive including friction modifier (HiTech 6437) to 10 Diethylamine or Triethylenetetramine Color Stabilizer 0.01-0.2 Based antiknock additive aromatic amines, including as a main component N-methylaniline rest

Also proposed is a fuel composition for gasoline-based internal combustion engines containing the above multifunctional additive in an amount of 0.3-3.0% wt.

The difference of the claimed technical solution is the content in the composition of the additive color stabilizer diethylamine or triethylenetetramine and detergent additives, including a friction modifier (HiTech 6437).

The use of a detergent additive in the composition, including a friction modifier and showing high anticorrosive properties in compositions with aromatic amines, allows the main engine elements to be kept clean.

The introduction of diethylamine or triethylenetetramine into the additive can increase chemical stability, which leads to color stabilization of the additive.

The additive can be used both to adjust the anti-detanation properties of marketable gasolines in the circulation system, restore their quality, and to develop a technology for the production of an assortment of high-octane motor gasolines that meet the requirements of the technical regulation.

The components used in the additive are industrial products.

In the proposed composition of the additive, it is preferable to use an aromatic amine (N-MA) with a minimal admixture of aniline having lower chemical stability and requiring the use of an antioxidant.

As an aromatic amine in a multifunctional additive, N-MA technical improved according to STO 00204168-001-2008 with a N-MA content of 98.0% wt. or an anti-knock additive based on aromatic amines ADA-SUPER according to STO 11605031-011-2007 with a N-MA content of 98.5% wt.

As the oxygenate used MTBE according to TU 38.103704-90 rev. 1-5.

Technical color diethylamine according to GOST 9875-88 or triethylenetetramine manufactured by AKZO NOBEL (Sweden) is used as a color stabilizer.

As a detergent additive, including a friction modifier, a Hi-tech 6437 additive manufactured by Afton Chemical (Great Britain) is used.

The additive HiTech 6437 is an oily liquid with a density at 15 ° C of 0.9134 g / cm ³ ; flash point (PMC) 60 ° C; pour point <-43 ° C; viscosity at 40 ° C 9.44 cSt.

In organic solvents, Hi-Tech 6437 forms a clear solution and is practically insoluble in water.

The proposed multifunctional additive is prepared by non-waste technology using standard equipment at a temperature of 15 ÷ 35 ° C by mixing the components to obtain a homogeneous solution.

To illustrate the claimed technical solution, 3 samples of the proposed additives were prepared, the composition of which is given in table 1.

The functional and operational properties of the prepared samples are given in table.2.

The effect of the additive on the detonation resistance was evaluated by the motor method according to ASTM D 2700-95 (GOST 511-82) at the UIT-85 installation according to the increase in the octane number of the reference mixture “70” of isooctane and n-heptane taken in the ratio of 70:30 (by volume) . The greater the increase in the octane number, the higher the antiknock properties of the additive. For the test samples, the increase is from 2.1 to 3.3 in comparison with the reference mixture.

The anticorrosive effectiveness of the additive was determined by the modified ASTM D 66 5 method in IT reference fuel (80% isooctane and 20% toluene by volume) in the presence of distilled water at a temperature of 38 ° C for 4 hours. In accordance with the recommendations of this method, to determine the degree of corrosion of the rod surface after testing, visual assessment criteria were adopted, according to which the maximum degree of corrosion (more than 5% of the surface of the rod is covered with corrosion products) is estimated at 3 points (this indicator was obtained for reference fuel IT) the surface of the rod, free from traces of corrosion (clean rod), is rated at 0 points; for test samples, this indicator is from 0 to 2 points.

The washing efficiency in assessing the tendency of motor gasoline to form deposits was determined by tests in bench conditions on a full-size VAZ 2101 engine according to the STO ANN 40488460-001-2004 method of the proposed additive samples in AI-95 gasoline in comparison with the original gasoline.

The washing properties of AI-95 gasoline with the proposed additive that does not contain the HiTech 6437 detergent additive, according to the STO ANN 40488460-001-2004 method, are 98 mg / valve. If the additive contains a HiTech-6437 detergent additive with a friction modifier, the washing properties of AI-95 gasoline will significantly improve (Table 2).

Assessment of the color of the additive after 1 year of storage was carried out visually and according to the ASTM D 1500 method. In accordance with the specified method, color assessment is carried out in ASTM units from 0.5 to 8 (from light yellow to dark brown). The more ASTM units, the darker the color of the product. From the results presented in table 2, it follows that after 1 year of storage, the color of the samples of the additive visually remained unchanged or slightly darkened (from light yellow to yellow). According to the ASTM D 1500 method, it was found that the color corresponds to from 1 to 4 units.

Thus, from the data presented in table 2, it can be seen that the developed additive in the claimed interval and ratio of components along with high antiknock, detergent and anticorrosive properties has color stability after 1 year of storage. The greatest efficiency in terms of washing, anti-detanation and anti-corrosion properties was shown by sample No. 1. In fuel compositions where stable components are mainly used and alcohols are not used, type 3 additive formulations can be added; it is advisable to introduce type 1 or 2 additive formulations in other compositions.

Using the proposed additives, laboratory samples of automobile gasolines of various component compositions of the Regular-92, Premium-95, Super-98 type were prepared (Table 3). Samples met the basic requirements of European standards and national Technical Regulations. At the same time, the use of additives in gasoline preparation technologies did not lead to any side effects on the physicochemical parameters regulated by the standard (Table 4).

Table 1 The composition of the samples of the proposed additives No. p / p Name of components The content of components in the samples,% wt. one 2 3 one MTBE twenty thirty 40 2 Diethylamine 0.2 - 0.01 3 Triethylenetetramine - 0.1 - four Detergent with friction modifier (HiTech 6437) 10.0 5,0 0 5 N-ma up to 100 up to 100 up to 100

table 2 Functional and operational properties of the samples of the proposed additives No. p / p The name of indicators The value of the indicators of the samples one 2 3 one The increase in the octane number of the reference mixture "70" at an additive concentration of C = 1% wt. 3.3 3,1 2.1 2 Anticorrosive effectiveness (degree of corrosion of the rod, points) at an additive concentration of C = 2.0% wt. in IT. 0 one 2 3 The washing efficiency, the mass of deposits, mg at an additive concentration of C = 2.0% wt. in commercial gasoline AI-95. 2.7 6.0 98 Color additives visually four source light yellow light yellow light yellow after 1 year of storage without change without change dark yellow Color according to ASTM D 1500 5 source 1,0 1,0 1,0 after 1 year of storage 1,5 2.0 4.0

Table 3 The composition of laboratory samples of high-octane gasolines obtained using the proposed multifunctional additives (mass fractions,%) No. p / p Component Name Regular 92 Premium 95 Super 98 one Catalytic Reform Gasoline 41 68 69 2 Catalytic Cracking Gasoline 39.5 10 four 3 Straight run fraction NK-85 ° С 9 2 0 four Gas petrol 9 12 5 5 Alkylate 0 0.5 6 6 MTBE (oxygenate) 0 5 fourteen 7 Suggested supplement 1,5 ** 2.5 *** 2.0 * Note. The content of aromatic hydrocarbons,% vol. 33 41 41.5 * - sample No. 3, see table 1 ** - sample No. 1, see table 1 *** - sample No. 2, see table 1

Table 4 Physico-chemical and antiknock indicators of laboratory samples of gasoline obtained using the proposed multifunctional additives No. p / p The name of indicators Norm (GOST R 51105) Regular 92 Premium 95 Super 98 one 2 3 four 5 6 one Knock resistance: octane number, not less than according to the research method 92.0 / 95.0 / 98.0 92.2 95.2 99.0 by motor method 83.0 / 85.0 / 88.0 83.0 85.3 88.0 2 Lead concentration, mg per 1 dm ^{3 of} gasoline, no more 5 lack of lack of lack of 3 L-5 Density at 15 ° С, kg / m ³ 725-780 749 765 776 four Mass fraction of sulfur,%, no more 0.0150 0.005 0.003 0.002 5 The concentration of resin washed with a solvent, mg per 100 cm ^{3 of} gasoline, not more than 5 1,0 0.8 1,5 6 Corrosion on a copper plate (3 hours at 50 ° C), units on a scale Grade 1 Grade 1 Grade 1 Grade 1 7 Appearance Transparent Transparent Transparent Transparent 8 Volume fraction of benzene,%, no more 5,0 0.8 1D 1D 9 Saturated vapor pressure (DNP), kPa 45-80 54 52 45 10 Fractional composition: volume fraction of evaporated gasoline,%, at temperature: 15-45 22 26 28 70 ° C 15-45 22 26 28 100 ° C 40-70 42 41 42 180 ° C, not less 85 94 96 96 The end of the boil of gasoline, ° C, not higher
The remainder in the flask,% vol., No more 215
2 200
1,0 200
1,0 200
1,0 eleven Evaporation Index (IPP) 1000 691 702 647

Table number 4

Physico-chemical and antiknock indicators of laboratory samples of gasoline obtained using the proposed multifunctional additives

Claims (2)

1. A multifunctional additive to motor gasoline, containing, wt.%:
Methyl tert-butyl ether 20-40 Detergent additive including friction modifier (HiTech 6437) to 10 Diethylamine color stabilizer or triethylenetetramine 0.01-0.2 Antiknock additive based on aromatic amines, including as primary component N-methylaniline rest 2. A fuel composition for gasoline-based internal combustion engines containing a multifunctional additive according to claim 1 in an amount of 0.3-3.0 wt.%.