RU2422495C2 - Additive to low-sulphur diesel fuel - Google Patents

Abstract

FIELD: oil and gas production.

SUBSTANCE: invention refers to additive improving wear resistant properties of low-sulphur diesel fuels. The additive contains distilled tall oil or fraction of fat acids of tall oil in mixture with quaternary ammonia derivatives on base of amines of tall oil at ratio from 0.66:1 to 4:1.

EFFECT: additive of enhanced wear resistant efficiency in diesel fuels.

2 cl, 3 tbl

Description

The invention relates to oil refining and petrochemicals, specifically to additives that improve the antiwear properties of low-sulfur diesel fuels. Ecologically improved low-sulfur diesel fuels produced in accordance with GOST 52368-2005 “Euro diesel fuel” are characterized by low lubricating properties, as a result of which the life of the fuel equipment is reduced. In order to ensure the necessary level of lubricating properties, antiwear additives are introduced into the fuel.

Known anti-wear additives for fuels containing naphthenic acids as active components (A.M. Danilov. Use of additives in fuels. M: Mir, 2005, 288 p.).

The disadvantage of these additives is the poor compatibility of the fuels containing them with engine oils and water. Such a requirement is mandatory for diesel fuels.

Additives based on the reaction products of mono - or polycarboxylic acids C ₂₄ -C ₆₅ and polyhydric (C ₂ -C ₁₀ ) alcohols (US Pat. Norway No. 169660, 1992, C10L 1/18), monoesters of dicarboxylic acids (A.S. USSR 458252, 1984, C10L 1/18), salts of an alkali or alkaline earth metal and polybasic acid (US Pat. USA 4804389, 1989 C10L 1/10; 1/29; NKI 44/70).

Closest to the claimed additive in composition and purpose is the additive, which is a tall oil acid (Bernaskot K., Germano L., Lopi J.-M., Maldonado P. Application of Russia 99107667/04, 2001).

The disadvantage of this additive is its relatively low anti-wear efficiency, as a result of which it is recommended in a relatively high concentration: more than 0.06% for fuel.

The present invention is the creation of additives with high anti-wear efficiency in diesel fuels.

To solve this problem, a composition of tall oil and additives of aliphatic amines and / or their derivatives are proposed in a weight ratio of (1-4).

The novelty of the proposed technical solution is the use of a mixture of tall oil and aliphatic amines and / or their derivatives, the components of which exhibit a synergistic effect. Previously, a similar composition was not used in fuels and was not offered. Its high anti-wear efficiency does not follow explicitly from known theoretical propositions.

Additionally, to improve physico-chemical properties and ease of use, the composition may contain a hydrocarbon solvent and a demulsifying additive used for its intended purpose. Moreover, the claimed ratio of tall oil and aliphatic amines and / or their derivatives is maintained.

The additive is obtained by sequentially mixing the calculated amounts of the above components at 20-50 ° C.

To illustrate the proposed technical solution, additive samples were prepared by mixing the above components with the following characteristics.

1. Tall oil is used in the following grades:

1.1. Distilled tall oil, TU 13-00281074-26-95.

Indicators Norm according to TU 13-00281074-26-95 Actually Appearance Light yellow to brown homogeneous liquid Acc. Density at 20 ° С, kg / m ³ 850-900 875 Mass fraction of the main substance,% Not less than 95 97 Flash point, ° С Not lower than 200 207 Pour point, ° C - Minus 7 Acid number, mg KOH / g Not lower than 140 164

1.2. Tall oil fatty acid fraction, GOST 14845-79.

Indicators Norm according to GOST 14845-79 Actually Acid number, mg KOH / g Not lower than 192 202 Flash point, ° С Not lower than 194 199 Mass fraction of resin acids,% No more than 2 1.4

2. Quaternary ammonium derivatives based on tall oil amines are produced according to TU 0257-007-35475596-98 with a change of No. 1.

Appearance A viscous liquid or amorphous mass of dark brown Acid number, mg KOH / g of product, not more than 25 Drop point, ° С, not higher 40 Amine number, g HCl per 100 g of product, not less than; 22

To illustrate the invention, prepared samples of additives (table 1):

Table 1 Additive Composition Samples Component one 2 3 four 5 6 7 8 9 Distilled tall oil,% wt. one hundred 80 60 fifty 40 - - - - Tall fatty acids,% wt. - - - - - 80 60 fifty 40 Quaternary ammonium derivatives based on tall oil amines 0 twenty 40 fifty 60 twenty 40 fifty 60 The ratio of the components: Prototype 4: 1 1: 0.66 1: 1 0.66: 1 4: 1 1: 0.66 1: 1 0.66: 1

The effectiveness of additives was tested in diesel fuel containing from 0.005 to 0.05% of the proposed additive according to the method of American standard ASTM D 6079, included in TU 38.401-58-296-2001 "Diesel automotive fuel". According to this method, a steel ball under a load of 20 kPa (0.2 kg / cm ² ) by means of a vibrator performs reciprocating movements with an amplitude of 1 mm and a frequency of 50 Hz along a plate placed in the test medium. Tests are carried out at temperatures of 60 and 25 ° C (it is taken into account that the fuel in the engine is in a heated state). The resulting wear spot is measured in two diameters (in the direction of travel and across) and the average is calculated. Then, an adjustment is made for temperature and humidity, and the final result D obtained is a characteristic of this sample. The accuracy of the method at 60 ° C: repeatability - 80 microns, reproducibility - 130 microns; at 25 ° С: repeatability - 110 microns, reproducibility - 170 microns. The norm of antiwear properties of diesel fuel according to EN-590 and TU 38.401-58-296-2001 is D≤460 microns.

table 2 Diameter of wear spots during fuel tests with additive compositions Example according to table 1 Concentration in fuel,% D, μm No additive - 562 1 (prototype) 0.01 512 2 0.01 418 3 0.01 362 four 0.01 333 5 0.01 458 6 0.01 411 7 0.01 358 8 0.01 322 9 0.01 460 1 (prototype) 0.005 500 four 0.005 398 8 0.005 405 1 (prototype) 0,025 480 four 0,025 321 8 0,025 315 1 (prototype) 0.05 452 four 0.05 348 8 0.05 345

Thus, sufficient additive effectiveness is manifested when the ratio of tall oil and quaternary ammonium derivatives based on tall oil amines is from 0.66: 1 to 4: 1, respectively. When these relations go beyond the bounds, the anti-wear efficiency of the additive decreases to unacceptable values. The proposed additive is effective in fuel already at a concentration of 0.005% wt. With increasing concentration, its effectiveness increases, but this dependence is not linear: with each portion of the additive, the increase in effect decreases.

Table 3 shows the physicochemical and operational characteristics of the additive of Example 6, in which a solvent (toluene) and a demulsifying additive (ethoxylated alcohol) are added.

Table 3 Indicators Actually The composition of the additive,%: Composition of tall oil and quaternary ammonium derivatives based on tall oil amines 74 Solvent (toluene) 25 Demulsifying additive one Physico-chemical characteristics: Acid number, g KOH / g 101 Pour point, ° C minus 27 Density, kg / m ³ 912 Operational properties of fuel with 0.01% additive: The diameter of the fuel wear spot, microns 410 Emulsifiability Does not form emulsions with water

Claims (2)

1. An additive that improves the antiwear properties of tall oil-based low-sulfur diesel fuels, characterized in that it contains distilled tall oil or a tall oil fatty acid fraction mixed with quaternary ammonium derivatives based on tall oil amines in a ratio of 0.66: 1 to 4 :one. 2. The additive according to claim 1, characterized in that it further comprises a hydrocarbon solvent and a demulsifying additive.