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

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

 

The invention relates to the field of oil refining and petrochemistry, particularly to a multifunctional additive to motor gasoline and fuel composition containing the additive.

Known widespread use in the compositions of gasoline antiknock additives on the basis of N-methylaniline (N-MA) (Amidaniel. The use of additives in fuels. Reference edition. M., Peace, 2005, p.20-30).

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

The additive is introduced into motor gasoline in concentrations up to 20 wt.%.

(U.S. Pat. Of the Russian Federation No. 2139914, 1999).

The disadvantage of this additive is a high methanol content, which increases its toxicity, absorption, and reduces the stability of gasoline during storage. Washing additive Automag effective for older gasoline engines and practically unsuitable for modern engines with direct fuel injection due to the low efficiency in removing resinous deposits on the intake valves and injectors.

Closest to the claimed is additive to the car Ben is Inam, containing, % wt.: a 6.5-70 N-MA, 0,2-27 tertiary butyl alcohol, not more than 6.0 detergent additive, 0.1 to 25 acetic acid esters and fusel oils and 100 MTBE. As a detergent additive use additive-containing condensation products of polyamine General formula NH2-(CH2)2-(NH-CH2-CH2)n-NH2where n=0-4, with C7-C20- fatty acids. The additive is intended for use in motor gasoline in concentrations up to 20 wt.%.

(U.S. Pat. Of the Russian Federation No. 2155793, 2000).

The lack of supplements is the presence of detergents with low thermal stability, which does not ensure the possibility of its application in the operation of injection internal combustion engines.

A significant drawback of the additive is also prone to color change during storage from light yellow to dark brown (color on the ASTM D 1500 from 0.5 to 8.0), and also to increase the quantity of deposits on the intake valves, especially the use of additives in gasolines containing products of cracking.

The task of the invention is to develop a multifunctional additive to motor gasoline based on aromatic amine having color stability during storage and high anti-knock, detergents and anti-corrosion properties, and fuel composition containing the additive./p>

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

Methyl tert-butyl ether20-40
Washing additive, including
friction modifier (Tech 6437)10
The stabilizer color diethylamine or Triethylenetetramine0,01-0,2
Antiknock additive based
aromatic amines, including
as a main component
N-methylanilinerest

Also offers a fuel composition for internal combustion engines on the basis of the gasoline containing the above-mentioned multifunctional additive in the amount of 0.3 to 3.0 wt.%.

The difference between the claimed technical solution is the content in the additive stabilizer color diethylamine or Triethylenetetramine and washing additives, including friction modifier (Tech 6437).

The use of the additive detergent additive comprising a friction modifier and showed high anti-corrosion properties in compositions with aromatic amines, allows you to keep the main elements of the engines.

The introduction of the additives diethylamine or Triethylenetetramine can improve chemical stability, which leads to stabilization of color additives.

The additive may be used to adjust antidetonation properties of commercial gasoline in the system of treatment, remediation, and development of production technology range of high octane gasolines that meet the requirements of the technical regulations.

Used in the additive components are products of industrial production.

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

As aromatic amine in a multifunctional additive use N-MA technical improvements over a HUNDRED 00204168-001-2008 with the content of N-MA 98,0% wt. or antiknock additive based on aromatic amines HELL-SUPER HUNDRED 11605031-011-2007 with the content of N-MA 98,5% wt.

As oxygenate use of MTBE in the Near 38.103704-90 var. 1-5.

As a color stabilizer use diethylamin technical GOST 9875-88 or Triethylenetetramine, manufactured by AKZO NOBEL (Sweden).

As a detergent additive comprising a friction modifier, use additive Tech 6437, manufactured by Afton Chemical (UK).

Additive high-Tech 6437 is an oily liquid with a density at 15°C 0,9134 g/cm3; flash point (PMC) 60°C; pour point <-43°C; viscosity at 40°C 9,44 cSt.

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

The proposed multifunctional additive is prepared by a waste-free technology with use of standard equipment at a temperature of 15÷35°C by mixing the components until a homogeneous solution.

To illustrate the proposed technical solution was prepared 3 sample of the proposed additions, the composition of which is summarized in table 1.

Functional and performance properties of the prepared samples are given in table 2.

The influence of additives on detonation resistance was estimated by the motor method according to the ASTM D 2700-95(GOST 511-82) on the installation FMP-85 to increase the octane number of the reference mixture "70" isooctane and n-heptane, taken in the ratio of 70:30 (by volume). The greater the increase in the octane number, the higher anted donazione properties of the additive. For the test samples, the increase is from 2.1 to 3.3 in comparison with the reference mixture.

Corrosion performance of the additive was determined by the modified method of ASTM D 66 5 in the reference fuel it (80% of 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 specified method for determining the degree of corrosion of the rod after the test adopted visual evaluation criteria by 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 figure is obtained for the reference fuel it); the surface of the rod, free from corrosion (clean rod), is valued at 0 points; for the test samples, the average is from 0 to 2 points.

The efficiency of the wash to assess the tendency of gasoline to the formation of deposits is determined by the test bench to full-size engine VAZ 2101 according to the method of HUNDRED ANNE 40488460-001-2004 offer samples of the additive in gasoline type AI-95 in comparison with the original gasoline.

Washing properties of gasoline AI-95 with the proposed Supplement containing detergent additive a Tech 6437, according to the method of HUNDRED ANNE 40488460-001-2004 be 98 mg/valve. In the presence of additive detergent additive High-6437 with modificato the om friction washing properties of gasoline AI-95 significantly improved (table 2).

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

Thus, from the data presented in table 2, it is seen that the developed additive in the stated interval and ratio of components along with high anti-knock, detergents and corrosion properties of a color-stable after 1 year of storage. The greatest efficiency detergent, antidetonation and anti-corrosion properties showed the sample No. 1. In the fuel composition, which is mainly used stable components and do not apply alcohol, you can enter the composition of the additive type 3 in the rest of the song, it is expedient to introduce samples of the additive type 1 or 2.

Using the proposed additives were prepared laboratory samples of gasoline different component composition type Regular-92, Premium-95, Super 98 (table 3). The samples were answered the main requirements of the European standards and national Technical regulations. The use of additives in the preparation technology of gasoline did not lead to any side effects on the physico-chemical characteristics of the regulated standard (table 4).

Table 1
The composition of the samples of the proposed additions
№ p/pName of the componentThe content of components in samples, % wt.
123
1MTBE203040
2Diethylamin0,2-0,01
3Triethylenetetramine-0,1-
4Washing additive comprising a friction modifier (Tech 6437)10,0 5,00
5N-MA100100100

Table 2
Functional and performance properties of samples of the proposed additions
№ p/pIndicesValue sample
123
1The increase in the octane number of the reference mixture "70" when the additive concentration=1% wt.3,33,12,1
2Corrosion performance (degree of corrosion of the rod points) when the additive concentration C=2.0% wt. in it.012
3The efficiency of the wash, dry mass of sediment (mg when the additive concentration C=2.0% wt. in the commodity be the Zina AI-95. 2,76,098
Color additives visually
4sourcelight yellowlight yellowlight yellow
after 1 year storagewithout changeswithout changesdark yellow
Color by the ASTM D 1500
5source1,01,01,0
after 1 year storage1,52,04,0

Table 3
The composition of La is oratorial samples of high-octane gasoline, obtained using the proposed multi-functional additives (mass fraction, %)
№ p/pComponent nameRegular-92Premium 95Super-98
1Catalytic reforming of gasoline416869
2The catalytic cracking gasoline39,5104
3Straight-run fraction of NC-85°C920
4Gas gas9125
5Alkylate00,56
6MTBE (oxygenate)0514
7The proposed additive1,5**2,5***2,0*
Note. The content of aromatic hydrocarbons, vol.%334141,5
* - sample No. 3, see table 1
** - sample # 1, see table 1
*** - sample # 2, see table 1

0,8
Table 4
Physico-chemical and anti-knock performance of laboratory samples of gasoline obtained using the proposed multi-functional additives
№ p/pIndicesNorm (GOST R 51105)Regular-92Premium 95Super-98
123456
Knock resistance: octane number, not less than on the research method92,0/95,0/98,092,2for 95.299,0
by the motor method83,0/85,0/88,083,085,388,0
2Lead concentration, mg / 1 DM3gasoline, not more than5nonono
3L-5 Density at 15°C, kg/m3725-780749765776
4Sulfur content, wt %, max0,01500,0050,0030,002
5The concentration of the resin is washed with a solvent, mg / 100 cm3gasoline, not more than51,01,5
6The effects of corrosion on the copper plate (3 h at 50°C), the units on the scaleClass 1Class 1Class 1Class 1
7AppearanceTransparent, netTransparent, netTransparent, netTransparent, net
8The volume fraction of benzene, %, max5,00,81D1D
9Vapour pressure (RVP), kPa45-80545245
10Fractional composition: volume fraction evaporated gasoline, %, temperature15-45222628
70°C 15-45222628
100°C40-70424142
180°C, not less than85949696
The end boiling point of gasoline, °C, not above
The residue in the flask, % vol., no more than
215
2
200
1,0
200
1,0
200
1,0
11Index volatility (IPP)1000691702647

Table No. 4

Physico-chemical and anti-knock performance of laboratory samples of gasoline obtained using the proposed multi-functional additives

1. Multifunctional additive to motor gasoline containing, wt.%:

Methyl tert-butyl ether20-40
Washing additive, including
friction modifier (Tech 6437)10
The stabilizer color diethylamine or
Triethylenetetramine0,01-0,2
Antiknock additive
on the basis of aromatic amines
comprising as a main
component N-methylanilinerest

2. Fuel composition for internal combustion engines on the basis of gasoline containing multifunctional additive according to claim 1 in the amount of 0.3 to 3.0 wt.%.



 

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4 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improvement of the method of alkylating diphenylamine, involving addition of isobutylene oligomers to diphenylamine in the presence of acid clay catalyst with formation of a mixture, and carrying out the reaction at temperature sufficiently low for preventing significant reduction of catalyst activity until completion of the said addition. Temperature is then increased, obtaining a mixture of alkylated diphenylamines, containing: 0.1 to 1% diphenylamine, less than 10% (tert-butyl)diphenylamine, less than 10% monooctyldiphenylamine, more than 20% dodecyldiphenylamine, more than 15% hexadecyldiphenylamine, less than 10% eicosenyldiphenylamine, less than 7% tetracosenyldiphenylamine, less than 4% octacosenyldiphenylamine and less than 2% polyisobutyldiphenylamine. The said diphenylamine is added to a mixture of olefins, containing fractions which are characterised by high reaction capacity, as well as fractions, which exhibit relatively lower reaction capacity, at temperature sufficiently low for preventing significant reduction of catalyst activity until the said addition is complete, and then latter at high temperature, obtaining a mixture of alkylated diphenylamines, where the given mixture contains not more than 27% products of alkylation with C8 chains or shorter, and more than 15% products of alkylation with C24 chains or longer, so as to increase rate of alkylation with participation of less reactive fractions. The invention also relates to the obtained mixture of alkylated diphenylamines, with antioxidant properties, and to a composition with antioxidant properties, containing A) an organic product, chosen from a group consisting of lubricant materials, hydraulic liquids, process oils, fuel and polymers, in amount of 90 to 99.5 wt %; and B) stabilising quantity of a mixture of alkylated diphenylamines from 0.05 to 10 wt %.

EFFECT: new compounds have useful biological properties.

13 cl, 3 dwg, 4 tbl, 4 ex

FIELD: oil and gas industry.

SUBSTANCE: method involves oil product sampling containing the detected number of token; at that, availability and quantitative content of token in the oil product is determined according to the availability of optical spectrum and intensity of spectrum lines in the wave-length region λ=350…600 nm without preliminary sample acidation and with the possibility of performing the flow analysis.

EFFECT: improving accuracy and fidelity, and simplifying identification process.

9 ex, 15 dwg

FIELD: chemistry.

SUBSTANCE: method involves addition to petrol of an additive - a product of condensation of boric acid, diethanolamine and fatty acids of plant oil of the C6-C20 fraction in molar ratio of 1:3:0.5 respectively in amount of 0.01-0.1 wt %.

EFFECT: method considerably reduces corrosiveness, pressure of saturated vapour and loss of petrol due to evaporation during prolonged storage and use.

8 ex, 2 tbl

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