Additive to hydrotreated diesel fuel

Abstract

FIELD: oil refining and petrochemistry.SUBSTANCE: additive to hydrotreated diesel fuel contains N-(1,3-dioxan-4-ylmethyl)-N,N-dimethylpropane-1,3-diamine, obtained by stirring N,N-dimethylpropylene diamine, 4-chloromethyl-1,3-dioxolane and triethylamine for 8 hours at a temperature of 100°C.EFFECT: improvement of wear-resistant and operational properties of diesel fuels.1 cl, 2 tbl

Description

[0001] The invention relates to oil refining and petrochemistry, specifically to an additive for hydrotreated diesel fuel (DF) that improves its lubricating properties.

[0002] It is known that during hydrotreating of diesel fuel, the lubricating capacity is significantly reduced due to the removal of organosulfur and polar compounds (N-, O-containing structures and heteroaromatic compounds) from the fuel, since they, in turn, form a protective layer on the metal surface.

[0003] There are additives based on the synthesis products of triethanolamine and polyhydric (OH more than 2 groups in the structure) alcohols (US Patent No. 4,599,090, C10L 1 / 22, 1986), monohydric alcohols (C 1-5 ) and primary amines of normal structure with a carbon skeleton from 8 to 50 atoms (US Patent No. 4,208,190, C10L 1 / 18; 1 / 22, 1980), unsaturated monocarboxylic acids and polyhydric alcohols (RF Patent No. 2,163,251, C10L 1 / 18, 1 / 22, 2001).

[0004] The disadvantage of the above-mentioned additives is the high cost of lubricating components; many polyhydric alcohols are scarce products.

[0005] There are additives that include paraffin hydrocarbons (from C) in their composition. 12 to C 30 ) and N-containing compounds (secondary and tertiary amines, amides, imides, QACs) (French application No. 2.510.598, C10L 1 / 22, 1983).

[0006] The disadvantage of the known composition is its ineffectiveness for use in the conditions of the Far North - it does not have the required low-temperature characteristics.

[0007] A known additive is a composition of organic acid esters, monocarboxylic acid amide, and alkylolamine, which we adopted as a prototype (RU Patent No. 2254358, published June 20, 2015). A disadvantage of this composition is its low lubricity (SDNI = 376 µm).

[0008] The technical problem solved by the proposed invention is the development of an additive to hydrotreated diesel fuel with the achievement of the following technical result: increasing the wear-resistant and performance properties of diesel fuels.

[0009] The technical result is achieved in that the additive to hydrotreated diesel fuel contains N-(1,3-dioxan-4-ylmethyl)-N,N-dimethylpropane-1,3-diamine, obtained by mixing N,N-dimethylpropylenediamine, 4-chloromethyl-1,3-dioxolane and triethylamine for 8 hours at a temperature of 100°C.

[0010] The novelty of the proposed technical solution is the creation of an additive containing (N-(l,3-dioxan-4-ylmethyl)-N,N-dimethylpropane-1,3-diamine), which at a concentration of 200 ppm (0.02%) in diesel fuel allows to increase the lubricating ability of diesel fuel. At the same time, the adjusted wear scar diameter (AWSD) is reduced to 343 µm from a value of 537 µm for diesel fuel (Table 1).

[0011]

[0012] Characteristics of the component for the preparation of an additive (added to diesel fuel):

[0013] Compound 1 (N-(1,3-dioxan-4-ylmethyl)-N,N-dimethylpropan-1,3-diamine): transparent liquid, bp = 262°C. NMR spectrum 1 H (δ, ppm, J / Hz): 1.52 (t, J=7.06, 2H, CH2CH2NH); 2.09 (s, 6H, 2 CH3N); 2.21 (t, J=7.08, 2H, CH2N); 2.48-2.59 (m, 2H, CH2NH); 2.62-2.68 (m, 2H, CH2CH), 3.51 (t, J=7.65, 1H, CH a CH2NH); 3.88 (t, J=7.06, 1H, CH2CH2NH); 4.41 (t, J=6.18, 1H, CHCH2NH); 4.75 (s, 1H, CH а O); 4.88 (s, 1H, CH а O). NMR spectrum 13 C (CDCl3, δ, ppm, J / Hz): 27.99 (CH2CH2N), 45.62 (2 CH3N), 48.30 (NCH2CH), 51.98 (CH2NCH2), 57.81 (CH2N), 67.94 (CHCH2O), 75.39 (CHCH2O), 95.09 (CH2O). Mass spectrum (EI), m / z, (I отн (%)): 188.09 (≤1) [M + ], 158.11 (15), 115.09 (40), 85.06 (75), 72.02 (70), 58.00 (100).

[0014]

[0015] The additive is obtained as follows.

[0016] A mixture of 2.4 g (20 mmol) of N,N-dimethylpropylenediamine, 10 mmol of 4-chloromethyl-1,3-dioxolane, and 10 ml of triethylamine was stirred on a magnetic stirrer for 8 h at 100°C. Upon completion of the synthesis (until complete conversion of 4-chloromethyl-1,3-dioxolane, monitored by GLC), the mixture was extracted with methylene chloride, dried, and evaporated. The target product (additive) was isolated by column chromatography, eluent hexane: ethyl acetate = 7:1.

[0017] The additive was then added dropwise to hydrotreated diesel fuel at a concentration of 200 ppm (0.02%) at room temperature until completely dissolved. To ensure homogeneity, the sample was stirred at 45°C for 10 minutes. The prepared mixture was tested immediately.

[0018] For each test, a new mixture was prepared with different concentrations.

[0019] The effectiveness of the additive was tested in diesel fuel using the method of the interstate standard GOST ISO 12156-1-2012 "Diesel fuel. Determination of lubricity using the HFRR apparatus."

[0020] The diameter of wear scars during fuel tests with additive compositions is presented in Table 2.

[0021]

[0022] Thus, the additive is already sufficiently effective at a concentration of 0.02% in diesel fuel. Beyond this concentration, its antiwear effectiveness decreases to unacceptable levels.

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