RU2078118C1 - Polyfunctional additive for hydrocarbon fuels for internal combustion engine and fuel composition comprising it - Google Patents

Abstract

FIELD: production of fuel compositions. SUBSTANCE: proposed additive comprises 0.5-10 % of product of interaction of aliphatic $$$ amine or aromatic $$$ amine, oxyethylated alkyl $$$ phenol (having 4-12 oxyethyl groups) with oxidized hydrocarbons or with monobasic fatty acids $$$ or with dibasic acids $$$ or mixture thereof, 7-94 % of aromatic amines, 0.1-2 % of shielding phenols or bis-phenols, 0.1-2 % of aminophenols and oxygenates. 4-oxydiphenylamine, 2,4,6-tri(dialkylaminomethyl) where alkyl is $$$ or products of condensation of ionol with amines are used as mentioned above additive. Methyl-tert-butyl ether, its mixture with isobutyl alcohol, with methyl alcohol, ethyl alcohol, with oil or dioxane alcohols are used as said oxygenates. Proposed fuel composition comprises hydrocarbon fuel and said additive, its quantity being 1-20 %. EFFECT: improved quality. 4 cl, 4 tbl

Description

 The invention relates to compositions of synergistic compositions of organic compounds, compositions of additives to motor gasolines to increase their octane number, washing, antioxidant, antiwear, antistatic and protective properties; thermal and colloidal stability of the fuel, as well as to fuel compositions containing this additive.

 Numerous additives known as antiknock organic compounds containing lead, iron, manganese, rare earth elements. These antiknock agents form deposits of the corresponding metals and their oxides in the engine and increase engine wear.

Homologues of C ₇ -C ₈ benzene (toluene, xylene, ethylbenzene), as well as low molecular weight aromatic amines (methylaniline, toluidine, xylidine, etc.) are also known as antidetonators of combustion regulators.

 So the additive is extraline containing aniline (up to 6 wt.), Dimethylaniline (up to 4.5 wt.) And the rest is methylaniline up to 100% TU 6.02.571-90.

 Additive compositions are also known containing low molecular weight aromatic amines and antioxidant additives such as ionol additive ADA (TU 38-401-58-61-93).

 The disadvantages of additives such as Extralin and ADA are their possibility of introducing into gasoline no more than 1 1.3% (after which there is a strong spasmodic increase in carbon formation in the engine), as well as the fact that these additives do not have detergents, antioxidants, antiwear, anti-static, water-retaining and protective properties.

 Oxygenates are also known as high-octane gasoline components: methyl or ethyl alcohol mixed with higher molecular weight alcohols; methyl tert-butyl ether (MTBE) and a mixture of 60 to 80% MTBE with 40 to 20% isobutyl alcohol product feterol.

The disadvantages of oxygenates are
the need to add them to gasoline in large quantities: to raise the octane number (O.Ch.) by 6 8 points 15-25 wt.

low hydrolytic stability and high moisture absorption capacity of oxygenates, leading to severe electrochemical corrosion of containers and the engine;
lower calorific value than gasolines and, therefore, reduced mileage at one gas station.

 Synergistic compositions of antidetonators such as aromatic amines, oxygenates and other surfactants; detergents, antioxidants, antiwear and protective (corrosion inhibitors) additives are unknown.

 The objective of the invention is to increase the antiknock properties (OH) of gasolines, increase their washing and protective properties, as well as increase their thermo-oxidative, chemical and colloidal stability in a wide temperature range due to the creation of a synergistic composition of surfactants - multifunctional additives for gasoline Remoin-BV, DB and Remoin -Fet.

 The problem is solved in that the additive contains, by weight.

Low molecular weight aromatic amine C ₆ -C ₈ 7 94
Shielded phenol or bisphenol 0.1 2
The reaction product of a C ₁₀ -C ₄₀ aliphatic amine or C ₆ -C ₈ aromatic amine with hydroxyethylated alkyl phenol with C ₈ -C ₉ alkyl and 4 to 12 hydroxyethyl groups; with oxidized hydrocarbons or with monobasic fatty acids C ₁₀ -C ₂₂ or with dibasic acids C ₄ -C ₂₀ or a mixture of reaction products 0.5 10
Aminophenols 0.1 2
Oxygenates up to 100
The fuel composition for internal combustion engines according to the invention contains 1 to 20 wt. the above additives and gasoline, gas gasoline (condensate) or a mixture of gasoline with aromatic compounds or with oxygenates.

As low molecular weight aromatic amines (A) C ₆ -C ₈ proposed
A-1 Extralin technical monomethylaniline TU 6.02-571-90, containing up to 6 wt. aniline, up to 4.5 wt. dimethylaniline and the rest up to 100% methylaniline;
A-2 Product ADA TU 38.401-58-61-93 with aniline content 1.5 1.7% dimethylaniline 0.3 0.5% additive Agidol-12 0.1-0.2% the rest monomethylaniline;
A-3 Xylidine;
A-4 Product SAMIN is a mixture of xylidine (50%), diethyl (25%) and triethylamine (25%).

 Small molecule amines are produced as commercial products by Volzhsky Orgsintez OJSC, Sintez OJSC, Dzerzhinsk, Chemical Plant of Berezniki, and other plants.

As shielded phenol or bisphenol are proposed:
F-1 Ionol GOST 10894-76, 2,6-ditretbutyl 4 butylphenol, other names DBK, Agidol-1;
F-2 Agidol-2 TU38.101.617-80, 2,2'-methylene bis (4 methyl-6 tert-butylphenol), another name is NG-2246.

As the reaction products (PV) of an aliphatic amine C ₁₀ -C ₄₀ or an aromatic amine C ₆ -C ₈ ; hydroxyethylated alkyl phenol with C ₈ -C ₉ alkyl and 4 to 12 hydroxyethyl groups; with oxidized hydrocarbons or with monobasic fatty acids C ₁₀ -C ₂₂ or with dibasic acids C ₄ -C ₂₀ or mixtures of reaction products are proposed:
PV-1 additive Minkor-2, TU 38.401969-93, the product of the interaction of oil oxidized with nitric acid, (TU 38.401656-87) of ethoxylated alkyl phenol neonol AF 9/12 according to TU 38.103625-85 and the aliphatic amine C ₁₇ -C ₂₀ according to TU 6.02- 740-79. Mol.mass 850 950; nitrogen at least 1% viscosity at 100 ^o C not more than 100 mm ² / s.

 PV-2 Additive AFEN TU 38.401.743-89 or AUTOMAG TU 38.401-58-33-92.

The reaction products of monobasic C ₁₀ -C ₂₂ fatty acids (oleic or stearic or FFA) with fatty amines or with polyethylene polymines (PEP), and OP-7 ethoxylated alkyl phenol (GOST 8433-81) in solvents (isobutyl alcohol, xylene or solvent). Molar mass 900 1200, density 820 900 kg / m ³ , acid number mg KOH / g not more than 20; alkaline number mg KOH / g not more than 40.

PV-3 additive Minkor-6
The product of the interaction of ethoxylated alkyl phenol OP-4 (TU 6.02.997-90) with maleic anhydride (GOST 5854-68) and with aliphatic amines C ₁₇ -C ₂₀ (TU 6-02-740-79). Like weight 1350 1550, nitrogen content 0.9-1.1% viscosity at 100 ^o C not more than 90 mm ² / s.

PV-4 additive Minkor-8
The product of the interaction of alkenyl succinic anhydride (dibasic acid C ₁₆ -C ₂₂ ) TU 6-14-04-108-90 with ethoxylated alkyl phenol OP-4 (TU 6.02.997-90) with aromatic amines C ₆ -C ₈ -technical extraline (TU 6.02.571-90). The molar mass is 1100-1200, the nitrogen content is more than 1.5%, the viscosity at 100 ^o C is not more than 50 mm ² / s.

PV-5 additive Minkor-10
The product of the interaction of alkenyl succinic anhydride (dibasic acid C ₁₆ -C ₂₂ ) TU 6-14-04-108-90 with ethoxylated alkyl phenol neonol AF 9/12 TU 38.103625-85 with aromatic amines C ₆ -C ₈ - Extralin according to TU 6.02.571 -90).

The technology for the production of interaction products (PV) consists in mixing the above components with vigorous stirring in stoichiometric-molar ratios to a weakly alkaline reaction of 3-4 hours at 60 95 ^o C (not higher than 100 ^o C).

 The intermolecular interaction is due to strong hydrogen bonds with the formation of H and P complexes.

As aminophenols (AF), 4-oxydiphenylamine, 2,4,6 tri (dialkylaminomethyl), where C ₁ -C ₄ alkyl; condensation products of ionol with amines. The following connections are checked:
AF-1 4-oxydiphenylamine, mol. weight 185.2; the nitrogen content of 7.6; so pl. 69.5 ^o C.

AF-2 2,4,6 tri (dialkylaminomethyl), where C ₁ -C ₄ alkyl, Manich bases obtained by formaldehyde condensation of phenol with respectively dimethyl, diethyl or dibutylamine of the general formula (C ₆ H ₂ ) OH [CH ₂ N (R ) ₂ ] ₃ . Like weight 400-520, nitrogen content of at least 8% t. bales. 160-210 ^o C at 10 mm Hg

Мол. масса 520-550, содержание азота 2,5-5% т.пл. 150-180^oC.AF-3 di [2,6 ditretbutyl-1 hydroxybenzyl] paraphenylamine, a condensation product of ionol with paraffinylenediamine or with paraphenicitin

Like weight 520-550, nitrogen content 2.5-5% mp 150-180 ^o C.

Methyl tert-butyl ether (MTBE), its mixtures with isobutyl alcohol (feterol), methyl alcohol, ethyl alcohol, X oil or dioxane alcohols are claimed as oxygenates. Oxygenate Compositions Tested:
OK-1 product of MTBE methyl tert-butyl ether, TU 38.103704-90;
OK-2 product fetol TU 301-03-008-94; a mixture of 60-80% MTBE with 0-40% isobutyl alcohol.

OK-3 mixture of MTBE or feterol with methyl or ethyl alcohol in the ratio of 1 part MTBE or feterol of 0.1-10 parts of alcohol;
OK-4 mixture of MTBE or feterol with methyl or ethyl alcohol in a ratio of 1 part MTBE or feterol of 0.1-10 parts of alcohol;
OK-5 mixture of MTBE or feterol with methyl or ethyl alcohol and oil X in the proportions: 1 part MTBE or feterol 0.1-10 parts of alcohol; 0.1-5 parts of oil X.

 Oil X (TU 113-03-476-82) is a by-product (waste) of caprolactam production, a multi-component product consisting of cyclohexanol (up to 20%), cyclohexanone (up to 40%) and cyclohexyl esters of various structures (up to 40%).

OK-6 mixture of MTBE or feterol with methyl or ethyl alcohol and dioxane alcohols in the ratios:
1 part MTBE or feterol 0.1-10 parts alcohol 0.1-5 parts dioxane alcohols.

"Dioxane alcohols" (TU 38.103.429-83) is a multicomponent waste product for the production of isoprene rubbers at SK plants, consisting of dioxane alcohols of the general formula C ₇ H ₁₄ O ₃ and polyols (triols) C ₆ H ₁₄ O ₃ . The by-products of the synthesis of isoprene from isobutylene and formaldehyde also include derivatives of 3-methyl-1,3-butanediol (MBD), 1,3 dioxanes, 2,6 dihydropyranes and other oxygen-containing compounds (more than 70).

 All these compounds are oxygenates, however, they require compounding with alcohols and MTBE according to the invention for compatibility with gasoline.

 Examples (compositions) of the formulations of multifunctional fuel additives Remoin BV, Remoin BD and Remoin-Fet according to the invention are presented in table. one.

The technology for the preparation of additives consists in mixing the components in devices with a mixing device at 40-80 ^o C with the desired homogenization (circulation) of the additive according to the "apparatus-pump-homogenizer-apparatus" scheme. The introduction of additives series "Remoin" in fuel (gasoline) in an amount of 1-20 wt. gasoline is carried out according to a similar scheme or by direct injection of the additive into reservoirs, tanks, containers with the desired circulation by the pump according to the “tank-pump-tank” scheme for better mixing.

 The scientific (theoretical) basis of the invention is the following phenomena.

 1. The proposed additive compositions are not a simple combination of surfactants, where each of them fulfills its functional role, but a synergistic composition, the synergistic effect of which is explained by intermolecular interactions of surfactants, which form additives and additives in gasoline with activated complexes of oscillators with resonant energy exchange through the centers of intermolecular interactions, P-complexes, H-complexes, complexes of long-lived free stable radicals (CSF) and secondary colloidal structures of complex structure units, micelles, and mixed micelles (5.6).

 2. It has been established that when a more polar component (MTBE, feterol and other oxygenates) is added to a less polar hydrocarbon medium (gasoline), the functional properties of the mixture, in particular, their octane number, volatility, freezing point, etc., do not obey the rules of additivity, but pass through extreme points with a certain increase (gain) in functional properties by a certain amount (due to the formation of activated complexes-oscillators).

 When additives and chemical polarizers are added to such a mixture, the extreme points are shifted toward a lower content of the polar component (oxygenates) and upwards, towards a significant increase in the increase in functional properties.

3. Thus, the following synergistic effects were established in the compositions proposed according to the present invention: shielded phenols or bisphenols and aminophenols synergistic thermostabilizing additives (shielded phenols are effective up to 120-140 ^o C, aminophenols up to 200 ^o C, mixtures in the temperature range 120-230 ^o C) mixtures of phenols and aminophenols; chemical polarizers (see paragraphs 1 and 2).

 interaction products (PV) detergents that reduce the deposition of resins and carbon deposits with aromatic amines; corrosion inhibitors; fast-acting, water-displacing and water-retaining components that inhibit oxygenates and eliminate their corrosiveness.

 aromatic amines and oxygenates antiknock additives; aromatic amines synergists, chemical polarizers oxygenates acid corrosion inhibitors; oxygenates amine synergists that improve their combustion process and reduce increased carbon formation due to aromatic amines.

In the table. 2-4 shows the results of tests of additives of extraline, ADA, oxygenates MTBE and feterol and examples of the proposed compositions of additives Remoin-BV, BD and Remoin-Fet in gasoline
Testing of additives for thermal oxidative stability (Table 2) was carried out according to the developed method: thermostat, special flasks with reflux condenser, air purge, 50 ml of the product, plates 10 and copper M-1, the test time is 6 hours at T = 95 ± 2 ^° C for 4 hours; and T = 230 ± 2 ^° C. 2 hours. Cooling 18 hours.

Tested additives in a concentration of 5 wt. in reference gasoline A-76. The color and acid number of gasoline with additives, the amount of deposits, and the corrosion of steel and copper plates in mg / m ^{2 were recorded} . The test results are presented in table. 2.

Claims (2)

1. A multifunctional additive for hydrocarbon fuels for internal combustion engines containing low molecular weight aromatic amines C ₆ C ₈ and shielded phenols or bisphenols, characterized in that it additionally contains the reaction products of an aliphatic amine C _{1 0} C _{4 0} or aromatic amine C ₆ - C ₈ , ethoxylated alkyl phenol with C ₈ C ₉ -alkyl and with 4 12 hydroxyethyl groups, with oxidized hydrocarbons, or with C _{1 0} C _{2 2} monobasic fatty acids, or C ₄ C _{2 0} dibasic acids or product mixtures action, and also additionally contains aminophenols and oxygenates in the following ratio of components, wt. Aromatic amines 7 94
Screened phenols or bisphenols 0.1 2
Interaction Products 0.5 10
Aminophenols 0.1 2
Oxygenates Up to 100
2. The additive according to claim 1, characterized in that it contains 4-hydroxyphenylamine, 2,4,6-tri (dialkylaminomethyl) as aminophenols, where C ₁ is C ₄ -alkyl, the products of the condensation of ionol with amines, and as oxygenates contains methyl tert-butyl ether, mixtures thereof with isobutyl alcohol, methyl alcohol, ethyl alcohol, oil or dioxane alcohols.  3. A fuel composition for internal combustion engines containing hydrocarbon fuel and an additive, characterized in that as an additive it contains 1 to 20 wt. multifunctional additives for PP. 1 and 2.

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