RU2494139C2 - Multifunctional gasoline additive and fuel composition containing said additive - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: modifying additive used is carbon nanomaterials, preferably in form of multilayer nanotubes in amount of 10^-6 to 10^-4 wt % per gasoline. The invention also relates to a fuel composition for an internal combustion engine, based on gasoline, which contains the multifunctional additive in amount of 0.3-3.0 wt %.

EFFECT: high octane number and operational properties of the gasoline.

3 cl, 2 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) (AM Danilov. The use of additives in fuels. Reference edition. M: Mir, 2005, p.20-30).

Also known is an additive to automobile gasolines based on methyl tert-butyl ether (MTBE), N-MA, methanol and detergent (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 motor gasolines in a concentration of up to 20% wt. (US Pat. RF No. 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 Avtomag detergent additive is effective for outdated carburetor engines and is practically unsuitable for modern engines with direct fuel injection due to the low efficiency in removing tar deposits on intake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.

An additive to motor gasolines is also known, 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, is a fatty acid. 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.

Closest to the claimed is an additive to gasoline 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 nano-materials "Taunit" from 10 ^-2 to 10 ^-5 Aromatic antiknock additive amines, including as a main component N-methylaniline rest.

Such a fuel composition may contain a multifunctional additive in an amount of from 0.3 to 3.0 wt.% (US Pat. RF No. 2400529, IPC C10L 1/18, C10L 1/185, C10L 1/22, C10L 1/10, 2010 .).

The disadvantage of the additive is the insufficient increase in the octane number (OCH), which does not provide the possibility of its use in the operation of internal combustion engines, including injection.

The objective of the invention is the development of a multifunctional additive to gasoline with high anti-knock properties, as well as a fuel composition comprising this additive.

To solve this problem, a multifunctional additive to motor gasoline is proposed containing antiknock and other components containing carbon nanomaterials (CNMs), preferably in the form of multilayer nanotubes (CNTs) in terms of gasoline in an amount of 10 ^-6 to 10 ^-4 wt.%.

A multifunctional additive to motor gasoline may contain, wt.%:

Modifying additive in the form of CNT “Taunit” in quantity from 10 ^-2 to 10 ^-5 Methyl tert-butyl ether 20-40 Detergent with modifier friction to 10 Diethylamine or Triethylenetetramine Color Stabilizer 0.01-0.2 Antiknock additive on aromatic amines - the rest, including as primary 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 proposed technical solution is the content in the composition of the additive carbon nanomatrials (CNM), preferably in the form of multilayer nanotubes (CNTs) in terms of gasoline in an amount of from 10 ^-6 to 10 ^-4 wt.%.

The use of a modifying additive in the form of carbon nanomaterials “Taunit” in terms of gasoline in the amount of 10 ^-6 to 10 ^-4 wt.% Provides:

- an increase of 04 by 9-11 units;

- effective removal of tar on inlet valves and injectors;

- improves the environmental safety of the use of gasoline due to more complete oxidation of the combustion products;

- provides fuel stability at low temperatures;

helps to reduce carbon formation due to their loosening.

The use of a detergent additive in the composition, including a friction modifier and showing high anticorrosion 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 antiknock 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 an 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. Hytec 6437 additive 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.

For testing, 000 “Nano Tech Center” (Tambov) samples of carbon nanotubes Taunit were provided, processed in a dry form in a disintegrator.

Technical characteristics of CNT "Taunit" are given in table 1

Table 1 No. p / p Characteristic Value one Outer diameter nm 20 ÷ 70 2 Inner Diameter nm 5 ÷ 10 3 Length, microns 2 and more four The total volume of impurities,% (after cleaning) Up to 5 (up to 1) 5 Bulk density, g / cm ³ 0.4 ÷ 0.6 6 Specific geometric surface, m ² / g 120-130 and more 7 Thermostability, ° С up to 600

To illustrate the claimed technical solution, 3 samples of the proposed additives were prepared, the composition of which is 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 for 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. Using the proposed additives were prepared laboratory samples based on 70% vol. i-octane and 30% vol. n-heptane.

The results of the test samples for OCh.

table 2 No. p / p Test sample (motor method) The composition of the test sample Och Growth OCh, units one Standard ETS mix 70% vol. i-octane 70.0 - 30% vol. n-heptane 2 Standard mixture + ADA 70% vol. i-octane 76.0 6.0 30% vol. n-heptane
1.5% wt. ADA 3 Standard mixture + ADA + CNT + X ₂ 70% vol. i-octane
30% vol. n-heptane
1.5% wt. ADA
10 ^-4 wt. CNT 81.3 11.3 four Standard mixture + ADA + CNT 70% vol. i-octane
30% vol. n-heptane
1.5% wt. ADA
10 ^-6 wt. CNT 79.5 9.5

From the data presented in table 2, it is seen that the developed additive in the claimed interval and the ratio of components has high antiknock properties. The highest efficiency in terms of antiknock properties was shown by sample 3. At the same time, with a significant decrease (almost 100 times) in the content of CNTs (sample 4), the efficiency of increasing 04 decreased by 25%.

Thus, the multifunctional additive to motor gasoline and the fuel composition containing it provide a 04 increase of 9-11 units. and improves the performance of gasoline.

Claims (3)

1. A multifunctional additive to motor gasoline containing antiknock and other components, characterized in that it contains carbon nanomaterials (CNM), preferably in the form of multilayer nanotubes (CNTs) in terms of gasoline in an amount of from 10 ^-6 to 10 ^-4 wt.%. 2. The multifunctional additive to motor gasoline according to claim 1, characterized in that it contains, wt.%:
Methyl tert-butyl ether 20-40 Detergent with friction modifier to 10 Diethylamine or Triethylenetetramine Color Stabilizer 0.01-0.2 Carbon Modifier nanomaterials “Taunit” from 10 ^-2 to 10 ^-5 Aromatic antiknock additive amines, including as the main component N-methylaniline Rest 3. 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.%.