RU2378323C1 - Addition to diesel fuel, and diesel fuel - Google Patents

Abstract

FIELD: oil and gas production.

SUBSTANCE: there proposed is addition to diesel fuel, which contains alkyl(C₃-C₂₀)nitrate, alkyl(C₁-C₂₅)succinimide, unsaturated fatty acid chosen from group of oleic, linoleic, linolenic, or amide of this acid and calcium sulphonate. In addition to the above components the addition also includes copolymer of highest ethers C₆-C₂₈ of acrylic or methacrylic acid with ethylenically unsaturated monomer. There also proposed is diesel fuel based on base fuel containing this addition in quantity of 0.001-1.0 wt %. As base fuel, the fuel includes gas condensate diesel fuel, summer or winter diesel fuel of oil origin. The proposed diesel fuel completely corresponds to requirements for diesel fuels by European Standard (EN 590) and new GOST R 52368-2005.

EFFECT: proposed addition allows improving start-up and low-temperature characteristics and greasy properties of diesel fuels.

3 cl, 2 tbl

Description

The present invention relates to the field of petroleum and gas chemistry, specifically to the composition of the additive to diesel fuel and diesel fuel of petroleum (DT) or gas condensate origin (GKDT) containing this additive.

Depressor additives are known to improve the low-temperature properties of DTs based on ethylene polymers, ethylene vinyl acetate copolymers or alkyl methacrylates, where alkyl contains 6-16 carbon atoms. (US Patent No. 4175926, C10L 1/18, 1979)

Known depressant additive to DT containing a copolymer based on ethylene with a molecular weight of 3.000-7.000 and amber succinic acid. (Japanese Application No. 59-8790, C10L 1/22, 1984)

However, these additives are not effective enough in diesel fuel used in the winter conditions of the Far North. In addition, they do not improve the starting properties of diesel fuel at low temperatures.

Known additive to diesel fuel containing 3-24% of a copolymer of ethylene with vinyl acetate with a molecular weight of 800-120.000; 4-41% alkyl nitrate with the number of carbon atoms in the alkyl group 4-16; 2-12% aliphatic alcohols C ₁ -C ₄ and 12-91% aromatic solvent with a boiling point of 135-288 ° C.

It also indicates that the additive is introduced into diesel fuel obtained from the corresponding fractions of petroleum products, oil shale and bitumen sands. (US Patent No. 4365973, C10L 1/22, 1982)

Known additive to diesel fuel, containing in wt.%:

Hydroxypropylated fatty alcohol C ₆ -C ₁₆ with a molecular weight of 300-2.000 5-15 Alkaline earth metal sulfonate 5-15 Alkyl methacrylate fraction copolymer C ₈ -C ₂₄ with molecular acetate vinyl acetate weighing 1.000-10.000 10-25 Alkyl (C ₃ -C ₁₈ ) Nitrate up to 100

(RF patent No. 2057790, C10L 1/18, 1/22, 1996)

The insufficiently high depressor ability of these additives limits their use in the composition of diesel fuel, for example, in extended-fractionated hydrocorticosteroids.

Also known is an additive to DT containing in wt%:

The copolymer of higher esters of C ₈ -C ₂₄ acrylic or methacrylic acid with ethylenically unsaturated monomer up to 90 Alkaline earth metal sulfonate no more than 10 Ethylene Alpha Olefin Copolymer molecular weight 1.000-20.000 up to 100

Additionally, the additive contains alkyl (C ₃ -C ₁₈ ) nitrate in an amount of 1-30% wt.

DT obtained on the basis of summer or winter DT grades containing the above additive in an amount of 0.001-0.5% wt. (RF patent No. 2119528, С10L 1/18, 1/22, 1998)

However, the known additive is not effective enough to affect the low temperature characteristics of diesel fuel.

Known additive to diesel fuel, containing in wt.%:

Alkyl (C ₃ -C ₂₀ ) Nitrate up to 55 Alkylsuccinimide where C ₁ -C ₂₅ alkyl 0.1-15 The copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with ethylenically unsaturated monomer up to 100

A diesel fuel based on base fuel containing the above additive in an amount of 0.01-0.8% by weight is also described there.

In this case, as the base DT contains GKDT expanded fractional composition or DT of oil origin. (RF patent №2280069, С10L 1/18, 1/22, 2005)

However, this additive, when used in low-sulfur diesel formulations, does not provide them with the required lubricating properties.

Closest to the claimed is an additive containing alkyl (C ₃ -C ₂₀ ) nitrate, alkyl (C ₁ -C ₂₅ ) succinimide, a copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with an ethylenically unsaturated monomer, unsaturated fatty acid selected from groups of oleic, linoleic, linolenic, or amide of this acid in the following ratio of components,% wt .:

Alkyl (C ₃ -C ₂₀ ) Nitrate up to 55 Alkyl (C ₁ -C ₂₅ ) Succinimide 0.1-15.0 The copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with ethylenically unsaturated monomer up to 60 Unsaturated fatty acid or its amide up to 100

It is also known DT based on the base fuel containing the above additive in an amount of 0.01-1.0% wt.

Moreover, as the base fuel contains GKDT expanded fractional composition or diesel fuel of petroleum origin. (RF patent No. 2320706, C10L 1/188, 1/196, 1/224, 1/23, 2006)

A disadvantage of the known additive is that it does not allow to improve the ecology of the air basin, reducing the content of harmful emissions in the air (ΔBB), which are also generated from the operation of automobile transport on diesel engines.

Currently, in the EU countries, as part of the implementation of environmental protection measures, the quality of diesel fuel is regulated by the European Standard EN 590, according to which the use of only low-sulfur diesel fuel of 3 types is provided. The content of sulfur compounds in DT of type 1 should be no more than 350 mg / kg, in DT of type 2 no more than 50 mg / kg and DT of type 3 no more than 10 mg / kg. However, despite the fact that when diesel engines operate on low-sulfur diesel fuel, emissions of harmful sulfur oxides will be reduced, which will certainly lead to an improvement in the environmental performance of diesel engines, low-sulfur diesel fuel has poor anti-wear (lubricating) properties, compared to high-sulfur fuels. To control and ensure the lubricating properties of DT, the indicator “wear spot diameter” is introduced in EN 590, the value of which should not exceed 460 microns. The norm for the “CC” indicator in the EU countries is at least 51 units. Finally, according to EN 590, according to EN 590, DTs are classified into 6 grades (A, B, C, D, E, F), which differ in terms of the “limiting filterability temperature”, which varies from plus 5 ° C for grade A to minus 20 ° C for grade F, with an interval between grades of 5 ° C. To meet the requirements for diesel fuel in Europe, you can use the appropriate additives. In Russia, starting from 2008, Decree of the Government of the Russian Federation No. 118 dated 02.27.08 introduced a new GOST R 52368-2005 (EN 590: 2004) “Euro diesel fuel. Technical conditions. " The new GOST, in contrast to the current GOST 305-82, is fully consistent with the European Standard, EN 590.

The present invention is the development of additives to diesel fuel and diesel fuel containing this additive, having improved starting, low temperature, lubricating properties and providing improved environmental performance of diesel engines.

To solve this problem, it is proposed to add to diesel fuel containing alkyl (C ₃ -C ₂₀ ) nitrate, alkyl (C ₁ -C ₂₅ ) succinimide, unsaturated fatty acid selected from the group of oleic, linoleic, linolenic, or amide of this acid and calcium sulfonate in the following ratio of components,% wt .:

Alkyl (C ₃ -C ₂₀ ) Nitrate up to 40 Alkyl (C ₁ -C ₂₅ ) Succinimide 0.1-10.0 Calcium sulfonate up to 20 Unsaturated fatty acid or its amide up to 100

In addition to the above components, the additive further comprises a copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with ethylenically unsaturated monomer in an amount of up to 20% wt.

It is also proposed diesel fuel based on the base fuel containing this additive in an amount of 0.001-1.0% wt.

As a base fuel contains GKDT, summer or winter diesel fuel of petroleum origin.

The differences of the proposed technical solution are in the additional content in the composition of the calcium sulfonate additive and in the ratio of components.

Despite the fact that all the components that make up the additive are known, industrial products, it is proposed to use them for the first time in the claimed ratio and combination. The ratio of components selected experimentally made it possible to obtain an additive having a complex of the required properties.

The use of the proposed additive in the composition of diesel fuel, both summer and winter brands, will increase the production of high-quality fuels that meet modern European standards. For the production of high-quality winter grades of winter grades based on summer grades, it is advisable to use an additive containing a copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with an ethylenically unsaturated monomer, which is responsible for improving the low-temperature properties of DT.

The proposed additive is prepared by mixing the components at room temperature and stirring for 0.5-2.0 hours

The additive is introduced into the composition of DT in the form of 5%, 10%, 35% and 50% concentrate in DT or another hydrocarbon solvent. In the prepared samples, the additive was introduced into the fuel in the form of a 35% concentrate in diesel fuel.

All components used for the preparation of additives are industrial products.

Component A is an alkyl (C ₃ -C ₂₀ ) nitrate, for example cyclohexyl nitrate, isopropyl nitrate, norbornyl nitrate. In the prepared additive samples, the least deficient 2-ethylhexyl nitrate was used.

Component B is alkyl (C ₁ -C ₂₅ ) succinimide. As alkyl succinimide, the additive C-5A or another succinimide additive of domestic or foreign production can be used. Alkyl (C ₁₆ -C ₁₈ ) succinimide was used in the additive samples.

Component B - oleic, linoleic or linolenic acid. To prepare additive samples, oleic acid (Example 1) and linoleic acid (Example 2) were used, and the use of linolenic acid leads to a similar result.

Component D - alkyl (C ₁ -C ₉ ) amides, alkylol (C ₁ -C ₁₂ ) amides, etc. can be used as amide of unsaturated fatty acid. Ethylamide (C ₂ ) linolenic acid (Example 3) and octylamide (C ₈ ) oleic acid (Example 4) were used in the prepared samples of the proposed additive. The use of other specified amides will allow us to expand the range of manufactured additives with improved starting, low temperature and lubricating properties.

Component D, a copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with an ethylenically unsaturated monomer, is the basis of industrial depressant additives for DT, such as PDP, EDEP-T, etc. In the preparation of additive samples, the base of PDP additive was used.

Component E - Calcium Sulfonate - Additive C-150, or C-300. In the preparation of additive samples used the additive C-150. The choice of calcium sulfonate as component E is due to the fact that sulfonates of other alkaline earth metals, for example barium or magnesium, when used in diesel fuel add toxic barium or magnesium oxides to the composition of the harmful emissions resulting from the combustion of diesel fuel. At the same time, calcium oxide formed using calcium sulfonate is not a toxic product. The effectiveness of improving the environmental performance of a diesel engine was judged by the indicator "number of explosives", which was measured using a portable instrument "BOSCH" connected to the exhaust pipe of an engine running on diesel fuel without additives and in the presence of additives. By reducing the "quantity of explosives" in the presence of an additive (ΔBB), we can conclude its effectiveness, in particular, in terms of "improving the environmental performance of a diesel engine."

The above method was prepared 6 samples of the proposed additives, the composition of which is given in table 1.

In addition, samples were prepared of the proposed diesel fuel containing 0.1% wt., Additives. Comparative tests of the prepared samples of diesel fuel and samples of the base fuel without additives are shown in table 2.

GKDT of a wide fractional composition, weighted with bottoms of stable condensate (GKDT "GShZ"), DT summer, grade "L" (DT "L") and DT winter, grade "Z-35" (DT Z- 35) of oil origin.

The data shown in table 2, confirm that the proposed additive can improve starting and low temperature characteristics and improve the lubricating properties of diesel fuel. The proposed DT fully complies with the requirements for DT Euro EN 590 and the new GOST R 52368-2005.

Table 1
The composition of the samples of additives No. p.p A,% wt. B,% wt. In,% wt. G,% wt. D,% wt. E,% wt. one. 10.0 0.1 79.9 0,0 5,0 5,0 2. 20,0 0.5 62.5 0,0 7.0 10.0 3. 25.0 1,0 0,0 64.0 10.0 0,0 four. 30,0 5,0 0,0 35.0 15.0 15.0 5. 35.0 7.0 41.0 0,0 17.0 0,0 6. 40,0 10.0 10.0 0,0 20,0 20,0 7. 40,0 0.1 39.9 0,0 0,0 20,0

table 2
The test results of diesel fuel with additives samples, the composition of which is given in table 1 No. p.p DT / DT with additive CC, units T-ra turbidity
T _p , ° C Solidification temperature T _s , ° C The ultimate filterability T _f , ° C ΔBB (compared to the base fuel),% The diameter of the wear spot, microns one. GKDT "GSHZ" 41 -31 -42 -32 - 530 2. GKDT "GShZ" + №1 51 -35 -48 -40 60 460 3. GKDT "GShZ" + №6 55 -37 -fifty -22 70 400 four. DT "L" 45 -5 -10 -6 - 620 5. DT "L" + №2 48 -5 -35 -17 60 420 6. DT "L" + No. 5 (comparative) 51 -5 -35 -16 - 540 7. DT "L" + №6 53 -5 -43 -22 75 380 8. DT "L" + No. 7 (comp.) 53 -5 -10 -6 75 390 9. DT "Z-35" 45 -25 -35 -27 - 540 10. DT "Z-35" + No. 3 (comp.) 47 -27 -40 -35 - 420 eleven. DT "Z-35" + №4 51 -32 -fifty -48 60 400 *) Additive samples were a 35% concentrate in diesel fuel;
**) The concentration of additive samples in diesel fuel is 0.1% wt.

Claims (3)

1. The diesel fuel additive containing alkyl (C ₃ -C ₂₀ ) nitrate, alkyl (C ₁ -C ₂₅ ) succinimide, unsaturated fatty acid selected from the group of oleic, linoleic, linolenic, or its amide, characterized in that it additionally contains calcium sulfonate in the following ratio of components, wt.%:
alkyl (C ₃ -C ₂₀ ) nitrate up to 40 alkyl (C ₁ -C ₂₅ ) succinimide 0,1-10 calcium sulfonate up to 20 unsaturated fatty acid or its amide up to 100 2. The additive according to claim 1, characterized in that it further comprises a copolymer of higher esters of C ₆ -C ₂₈ acrylic or methacrylic acid with ethylenically unsaturated monomer in an amount up to 20 wt.%. 3. Diesel fuel based on base fuel containing an additive, characterized in that it contains the additive according to claim 1 in an amount of 0.001-1.0 wt.%.