RU2254358C1 - Hydrocarbon fuel additive - Google Patents

Abstract

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: additive improving lubricating properties of hydrocarbon fuels, in particular diesel fuels, contains: 90-99% of monocarboxylic acid aminoalkyl ester of general formula R-CO-O-C₂H₄-NR₁R₂, wherein R represents isoparaffinic, olefinic, or alkylcycloparaffinic hydrocarbon radical containing 10-30 carbon atoms, R₁ and R₂ represent hydrogen atom, methyl, ethyl, hydroxyethyl, or group -C₂H₄O(O)-C-R; 0.5-19.5% of esteramide of monocarboxylic acid and alkylolamine of general formula R-CO-N(R₁)C₂H₄O-CO-R, wherein R is as above and R₁ hydrogen atom, hydroxyethyl, or group -C₂H₄O(O)-C-R; 0.5-2% of amide of monocarboxylic acid and alkylolamine of general formula R-CO-NR₁R₂, wherein R is as above, R₁ hydrogen atom, R-CO-, or -C₂H₄OH, and R₁ hydrogen atom or -C₂H₄OH.

EFFECT: enabled production of environmentally safe low-sulfur fuel exhibiting high antiwear properties.

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Description

The present invention relates to the field of oil refining and petrochemicals, specifically to an additive designed to improve the lubricating properties of hydrocarbon fuels, in particular diesel fuels.

It is known that with a decrease in sulfur content in hydrocarbon fuels, in particular diesel fuels, their lubricating properties are significantly deteriorated, and antiwear additives are required in these fuels.

There are no domestic antiwear additives used in motor fuels. For these purposes, additive K is introduced into jet fuels, which is naphthenic acids released from the oils of the Baku fields. Among the imported additives are approved such as Hitec-586 (for jet fuels) and Paradine-665 (for diesel fuels).

(AM Danilov. "The use of additives in fuels for automobiles", Moscow, Chemistry, 2000, p.172-175).

From the patent documentation it is known that in order to improve the antiwear properties of hydrocarbon fuels, for example diesel, monoatomic C ₁ -C ₅ alkanols and an effective amount of primary normal aliphatic amine RNH ₂ , where RC ₈ -C ₅₀ is alkyl or alkenyl, are introduced. (US Patent No. 4208190, C 10 L 1/18, 1/22, 1980); the product of the interaction of maleic acid and 2,5-dimercapto-1,3,4, -triazole in an amount of 0.001-2% (US Patent No. 4880437, C 10 L 1/10, 1989); the reaction product of tert-aminoalkanol, for example triethanolamine, with a compound of the formula R (OH) _x , where R is an aliphatic radical, x≥1. (U.S. Patent No. 4,599,090, C 10 L 1/22, 1986)

It is also known to use antiwear additives for diesel fuels, which are one or more esters of monocarboxylic acid and mono- or polyhydroxyalcohol (RF Patent No. 2161640, C 10 L 1/18, 2001); a mixture of esters: a) an ester of an unsaturated monocarboxylic acid and a polyhydric alcohol; and b) an ester of an unsaturated monocarboxylic acid and a polyhydric alcohol containing at least three hydroxyl groups, and the esters (a) and (b) are different (RF Patent No. 2158750, C 10 L 1/18, 2000); or composition a) of a paraffin dispersant — an acylated compound of nitrogen and a carboxylic acid, or monocarboxylic acid, or a monocarboxylic acid ester of alcohol, where the acid contains 2-50 carbon atoms and the alcohol contains one or more carbon atoms (RF Patent No. 2163251, C 10 L 1/18, 1/22, 2001).

All proposed additives as a component providing lubricating properties contain esters of polyhydric alcohols, in particular glycerol, which is an expensive scarce product. In addition, some of the proposed additives have poor compatibility with motor oils.

Closest to the claimed composition and the achieved result is an antiwear fuel additive, which is a mixture containing 5-25% wt. glycerol monoester R ₁ —C (O) —O — CH ₂ —CHO — CH ₂ OH or R ₁ —C (O) —OCH (CH ₂ OH) ₂ , where R ₁ is an alkyl chain containing from 8 to 24 carbon atoms, or a mono- or polycyclic group containing from 8 to 60 carbon atoms; 35-75% wt. compounds of the formula R ₂ -C (O) -X, where R ₂ is a linear or slightly branched saturated or unsaturated alkyl chain containing from 8 to 24 carbon atoms, X is a C ₁ -C ₈ hydrocarbon radical, optionally substituted with one or more ester groups, or derivatives of primary or secondary amines and alkanolamines of an aliphatic hydrocarbon chain containing from 1 to 18 carbon atoms and 0.1-20% wt. glycerol diester. To obtain these components, natural acids of plant or animal origin are used. (RF patent №2167919, С 10 L 1/22, 2001)

The disadvantages of the known additives are low anti-wear properties, as well as the use of expensive scarce products in its production: glycerin and carboxylic acids of vegetable or animal origin.

The objective of the invention is to develop additives to low-sulfur hydrocarbon fuels based on available petroleum or synthetic products, providing high anti-wear properties and having good compatibility with engine oil.

To solve this problem, an additive to hydrocarbon fuel based on esters of organic acids is proposed, which differs from the known ones in that it contains 80-99% wt. monocarboxylic acid ester and alkylolamine of the formula R — C (O) —O — C ₂ H ₄ —N (R ₁ ) R ₂ (1), where R is an isoparaffinic, olefinic or alkylcycloparaffinic hydrocarbon radical containing from 10 to 30 carbon atoms , R ₁ , R ₂ —H, —CH ₃ , —C ₂ H ₅ , —C ₂ H ₄ OH, or C ₂ H ₄ O (O) —CR; 0.5-19.5% wt. an ester of monocarboxylic acid and an alkylolamine of the formula RC (O) -N (R ₁ ) C ₂ H ₄ O- (O) CR (2), where R is an isoparaffin, olefin or alkylcycloparaffin hydrocarbon radical containing from 10 to 30 carbon atoms, R ₁ — H, —C ₂ H ₄ OH or —C ₂ H ₄ O (O) —CR; and 0.5-2% wt. monocarboxylic acid amide and alkylolamine of the formula RC (O) -N- (R ₁ ) (R ₂ ) (3), where R is an isoparaffin, olefin or alkylcycloparaffin hydrocarbon radical containing from 10 to 30 carbon atoms, R ₁ - H, - C ₂ H ₄ OH or —C (O) —R, R ₂ —H or —C ₂ H ₄ OH.

The proposed combination of components taken in the stated ratio is new and allows you to get an effective anti-wear additive to hydrocarbon fuels, in addition, having good compatibility with motor oils. All products used to obtain the components of the proposed additives are not scarce, since their production has been mastered on an industrial scale.

To obtain the products used as components of the proposed additives, alkylamines such as methyldiethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine can be taken. Acids of petroleum origin can be used as organic acids: distilled naphthenic acids with an acid number of 200-270 mg KOH / 1 g (DNA), asidols or synthetic acids: higher isomeric acids with a molecular weight of 250-450 (VIC), oleic acid (OK ) other.

Esters, ethers and amides of formulas 1, 2 and 3 are obtained by known methods: by esterification, transesterification or condensation. The proposed additive can be obtained by mixing its constituent components: esters, ethers and amides of monocarboxylic acid and alkylolamine in the claimed ratio or directly by condensation of a mixture of monocarboxylic acids and a mixture of alkylolamines, taken in ratios that provide an additive of the claimed composition.

To illustrate the claimed technical solution, 5 additive samples were prepared, the composition and characteristics of which are given in tables 1 and 2.

The prepared samples were tested in low-sulfur diesel fuel, the sulfur content of which was 0.034%. The antiwear properties of the additive samples were evaluated according to ISO 12156 on an HFRR instrument. The test results are shown in table 3. As can be seen from the data presented, the addition of the proposed additives in low sulfur diesel fuel at a concentration of 0.01-0.02% wt. significantly improves its lubricating properties.

The compatibility of the additive with engine oil (SAE 15 w-40cF-4 / SF) was evaluated by the method of DGMK 531 1-A. Table 4 shows the results of evaluating the compatibility with the oil for the additive sample of example 4. The data presented show that the proposed additive is compatible with engine oil. Other additive samples give similar results.

In addition to diesel fuels, the proposed additive can be used to improve the lubricating properties of other hydrocarbon fuels, such as low-viscosity marine, jet, etc.

Using the proposed additives will allow you to get environmentally friendly hydrocarbon fuels with a low sulfur content, with high anti-wear properties.

Table 1
The composition of the samples of the proposed additives No. Name Content,% wt. component and its characteristics Example for example Example for example Example for example Example for example Example for example 1 2 3 4 5 1 Monoester of OK and methyldiethanolamine (r.h. = 3.0 mg KOH / g; n.h. = 110 mg KOH / g) 99 - - - - 2 Monoester of DNA and triethanolamine (c.h. = 3.9 mg KOH / g; n.h. = 108 mg KOH / g) - 80 - - 95 3 Diester of DNA and triethanolamine (c.h. = 3.4 mg KOH / g; n.h. = 76 mg KOH / g) - - 90 - - 4 Mono-ester of VIC and triethanolamine (r.h. = 2.8 mg KOH / g; n.h. = 98 mg KOH / g) - - - 90 - 5 Ether of DNA and diethanolamine (c.h. = 10.2 mg KOH / g; n.h. = 1.5 mg KOH / g) 0.5 eighteen nine 8 4,5 6 Amide VIC and diethanolamine (r.h. = 5.3 mg KOH / g, n.a. = 143 mg KOH / g) 0.5 - - - 0.5 7 Amide DNA and monoethanolamine (c.h. = 3 mg KOH / g, n.h. = 167 mg KOH / g) - 2 1 2 -

Table 3.
The results of the evaluation of antiwear properties of samples of the proposed additives No. Sample Name The diameter of the wear spot, microns Reducing the diameter of the wear spot,% 1 Original diesel fuel with a sulfur content of 0.034% (DT) 576 2 Diesel fuel + 0.02% additive in example 1 403 thirty 3 Diesel fuel + 0,015% additive according to example 2 376 35 4 Diesel fuel + 0.01% additive according to example 3 407 thirty 5 Diesel fuel + 0.01% additive according to example 4 438 24 6 Diesel fuel + 0,015% additive according to example 5 389 34

Table 4
Oil Compatibility Assessment Results (SAE 15 w-40cF-4 / SF Motor Oil) No. Name of state Diesel source Original diesel fuel + engine oil Starting diesel fuel + 0.015% additive according to example 4 + oil Oil / Additive Mixture 1 Appearance (immediately after mixing) transparent transparent without sediment Transparent oil color 2 Appearance (after 3 days and cooling for 1 hour) - - Transparent oil color 3 Appearance (after adding diesel fuel up to 500 ml) - - Transparent - 4 Filtration time (sec.) By SEDAB method 90 100 110 - 5 Filtered fuel, cm ³ 500 510 520

Claims (1)

Additive to hydrocarbon fuel based on esters of organic acids, characterized in that it contains 80-99 wt.% Ester of monocarboxylic acid and alkylolamine of the formula RC (O) -O-C ₂ H ₄ -N (R ₁ ) R ₂ ( 1), where R-isoparaffin, olefin or alkylcycloparaffin hydrocarbon radical containing from 10 to 30 carbon atoms, R ₁ , R ₂ - H, -CH ₃ , -C ₂ H ₅ , -C ₂ H ₄ OH or -C ₂ H ₄ O (O) -CR; 0.5-19.5 wt.% Monocarboxylic acid and alkylolamine ester amide of the formula RC (O) -N (R ₁ ) C ₂ H ₄ O- (O) CR (2), where R is isoparaffinic, olefinic or alkylcycloparaffinic hydrocarbon radical containing from 10 to 30 carbon atoms, R ₁ —H, —C ₂ H ₄ OH or C ₂ H ₄ O (O) —CR; 0.5-2 wt.% Monocarboxylic acid amide and alkylolamine of the formula RC (O) -N- (R ₁ ) (R ₂ ) (3), where R is isoparaffin, olefin or alkylcycloparaffin hydrocarbon radical containing from 10 to 30 atoms carbon, R ₁ —H, —C (O) —R, —C ₂ H ₄ OH; R ₂ —H or —C ₂ H ₄ OH.