RU2756770C1 - Depressor-dispersing additive for diesel fuels and method for production thereof - Google Patents

Abstract

FIELD: petroleum industry.

SUBSTANCE: invention relates to the field of petroleum processing and petrochemistry, in particular, to a composition of a depressor-dispersing additive for diesel fuels. A depressor-dispersing additive for diesel fuels containing a mixture of a depressor and a dispersing component in a solvent, wherein a modified copolymer of maleic anhydride and alpha-olefins by the general formula (I) is used as a depressor component, wherein R₁ is selected from hydrocarbon groups containing from 6 to 30 carbon atoms, and X and Y can be hydroxyls and(or) residues of amines or alcohols, or a mixture thereof, with a length of the alkyl radical C₆ to C₂₈, obtained by means of a reaction of a radical copolymerisation of maleic anhydride and a fraction of alpha-olefins C₆ to C₃₀ in the presence of a radical polymerisation initiator in a corresponding solvent, and further modification of the resulting copolymer with fatty amines or alcohols, or a mixture thereof, with the length of the alkyl C₆ to C₂₈, characterised by containing a bivalent compound obtained by means of a reaction of a multi-stage functionalisation of a rigid frame adamantane molecule producing a final product of 1,3,5-trialkylamide-7-aminoadamantane by the general formula (II) as a dispersing component, wherein R is selected from hydrocarbon groups containing from 6 to 26 carbon atoms, with the following ratio of components, % wt.: dispersing component from 3 to 30% wt., depressor component from 35 to 70% wt., solvent from 25 to 60% wt.

EFFECT: improvement in the operational characteristics of the diesel fuel, reduction in the extreme filterability temperature of the diesel fuel by 10 to 23°C, ensured sedimentation stability during cold storage thereof.

2 cl, 1 tbl, 7 ex

Description

Technology area

This invention relates to the field of oil refining and petrochemistry, in particular to the composition of a depressant-dispersant additive (DPA) for diesel fuels (DF).

State of the art

It is known that paraffins contained in middle distillates crystallize at low temperatures and form a precipitate either during storage of distillates, or during their transportation in tanks, or when they are used in diesel engines, as well as in industrial or domestic boilers. In view of the fact that the crystallization temperature of paraffins is a limiting factor when using the mentioned middle distillates, it is customary to add additives to them, which make it possible to obtain their adaptation to the temperature of use and storage.

It has long been known that suitable additives can modify the growth of n-paraffin crystals in middle distillate fuels. The additives with good efficiency prevent the middle distillate fuel from solidifying at a temperature several degrees Celsius below the temperature at which the first wax crystals crystallize. Instead, well-crystallizing, individual wax crystals are formed, which also pass filters in motor vehicles and heating systems with a further decrease in temperature, or at least one permeable sludge for the liquid portion of the middle distillates, so that trouble-free operation is ensured.

The indicators characterizing the low-temperature properties of diesel fuel are the limiting filterability temperature (t _f ), the pour point (t _s ) and the cloud point (t _p ). The index t _f determines the minimum temperature at which diesel fuel is able to pass through the pores of the fuel filtration system. The indicator t _z determines the temperature at which the diesel fuel completely loses its mobility, that is, it freezes. The t _p index reflects the temperature of the onset of crystallization from diesel fuel of hydrocarbons belonging to the class of n-paraffins. This is the temperature at which the fuel "becomes cloudy".

As shown by numerous studies carried out over the past 30 years with depressants, most depressants of various chemical structures effectively reduce the t _{s of} diesel fuel, both summer and winter grades. In this case, only depressants with a certain chemical structure, such as polyalkyl methacrylates, polyalkyl acrylates, as well as copolymers of higher alkyl esters of acrylic or methacrylic acid, for example, with vinyl acetate or acrylonitrile _{, can affect t p.} But even these depressants are capable of lowering t _p DT only of winter varieties and only by 3-5 ° C. Taking all this into account, for the successful practical application of depressants, it is necessary to develop such additives that could effectively reduce precisely t _f DF. A decrease in this indicator, with the help of depressors, will prevent clogging of the filters of the fuel system of a diesel engine when the ambient temperature drops and thus ensure its uninterrupted operation in various climatic conditions. To increase the aggregate (resistance of a heterogeneous dispersed system to coagulation processes) and sedimentation (resistance to sedimentation of particles of the dispersed phase) stability of diesel fuel at negative temperatures, in recent years, depressants began to be used together with other additives called "n-paraffin dispersants", that is with additives with a dispersing effect.

As a rule, depressant-dispersant additives are compositions consisting of components of various functional purposes: the depressant component is responsible for lowering _tf and _tf DF, and the dispersing component prevents the n-paraffins crystallizing from fuels at low temperatures from uniting into large aggregates and, thus Thus, it contributes to the preservation of the aggregate stability of the diesel fuel at temperatures below its t _p .

A depressant additive is known from the prior art to improve the low-temperature properties of mid-distillate fuels (see US patent No. 20200017786 dated 01.16.2020), containing copolymers of unsaturated anhydride, polymerized with alkyl-α-olefins, and further grafted with phenylalanol or alkoxylate, fatty alcohol and a primary or secondary fatty amine.

Also, a known depressant additive for improving the low-temperature properties of mid-distilled fuels (see US patent No. 20190203135 dated 04.07.2019), containing the reaction product of a copolymer of maleic anhydride with alpha-olefins and an aliphatic tertiary amine.

Known depressant additive according to US patent No. 20030163951 from 04.09.2003, consisting of copolymers of a dicarboxylic compound with an olefin, to which nitrogen-containing groups and / or esters of the general formula are grafted

where R ₁ and R ₂ and R ₄ and R ₅ , R ₃ and R ₆ are hydrogen or alkyl radicals, and X is selected from amine salts and N-alkyl polyalkylene polyamines and their monohydroxylated and polyhydroxylated derivatives, alkyl esters and esters N -alkylpolyalkylenepolyamine and alkylamines. and N-alkylpolyalkylenepolyamines.

The disadvantage of the above additives is the impossibility of ensuring sedimentation stability during cold storage of fuel, due to the absence of a dispersing component.

Known additive to diesel fuel (see patent RU No. 2320706 from 27.03.2008), containing alkyl (C ₃ -C ₂₀ ) nitrate up to 55 wt.%, Copolymer of higher esters of C ₈ -C ₂₈ acrylic or methacrylic acid with ethylenically unsaturated monomers up to 60 wt.% and as a dispersing component alkyl (C ₁ -C ₂₅ ) succinimide 0.1-10 wt.%, an unsaturated fatty acid selected from the group oleic, linoleic or lenolenic, or its amide up to 100 wt.%. The additive is used in an amount of 0.01-1.0 wt%.

The disadvantage of this additive is that the additive is a complex mixture of components, for which expensive monomers are used. In addition, the sedimentation stability of diesel fuel with an additive during its cold storage has not been declared, and a relatively low depression of the maximum filterability temperature of diesel fuel when the additive is added to it is noted.

The closest in essence and the achieved technical result is a depressant-dispersant additive for diesel fuel (see patent RU No. 2684412 dated 09.04.2019), in which a polymer compound obtained by the reaction of radical copolymerization of maleic anhydride and fraction 1- is used as a depressant component. olefins C ₈ -C ₂₄ with the participation of a radical polymerization initiator, with a starting reagent ratio from 1: 0.92 to 1: 3.7 at a temperature of 75-90 ° C for 8-23 hours in an appropriate solvent, after which the solvent is evaporated and the target product is isolated, and as a dispersing component is a polymer compound obtained by the reaction of metathesis copolymerization of functionalized norbornene and synthetic divinyl rubber and 1-hexene or 1-octene in the presence of a metal complex dialkyl ruthenium catalyst in an appropriate solvent, with a ratio of functionalized norbornene: rubber 15 to 1: 1, ratio and catalyst: olefins in the reaction mixture from 1: 350000 to 1: 10000, at a temperature of 25-70 ° C for 8-23 hours, then the reaction mixture is hydrogenated with hydrogen at a pressure of 5-10 atm in the presence of palladium, then filtered through alumina and the filtrate is evaporated, and the depressant and dispersant components are in the additive in a ratio of 3: 7 to 7: 3 by volume.

The disadvantage of this additive is the special requirements for the molecular weight distribution of n-paraffins of the fuel to ensure the sedimentation stability of the fuel, which leads to the non-universality of the additive in relation to fuels with different molecular weight distribution.

A significant difference of the claimed additive is the use as a dispersing component of a bivalent compound on a platform of a rigid framework molecule, for example, adamantane, which, due to the presence of spatially preorganized groups and radicals, has a high affinity to the surface of paraffin crystals, which ensures a high charge on their surface and, thereby preventing their agglomeration. By varying the length of alkyl radicals in the dispersant molecule, it is possible to achieve effective adsorption on the surface of crystals of paraffins of middle distillates of different composition. In other words, this dispersant component makes it possible to increase the efficiency and versatility of the inventive additive.

Disclosure of invention

The objective of the invention is to provide an effective depressant-dispersant additive for diesel fuel, which has versatility in relation to the composition of middle distillates.

The technical result of the invention is to improve the performance of diesel fuel, to reduce the limiting temperature of the filterability of diesel fuel by 10-23 ° C, to ensure sedimentation stability during cold storage.

The task and the technical result is achieved by the fact that a depressant-dispersant additive for diesel fuel is obtained, containing as a depressant component a modified copolymer of maleic anhydride and alpha-olefins of general formula (I)

where R _{1 is} selected from hydrocarbon groups containing from 6 to 30 carbon atoms, and X and Y can be hydroxyls and (or) residues from amines or alcohols, or a mixture thereof, with the length of the C ₆ -C ₂₈ alkyl radical obtained by reaction radical copolymerization of maleic anhydride and a fraction of C ₆ -C ₃₀ alpha-olefins with the participation of a radical polymerization initiator in an appropriate solvent, and the subsequent modification of the resulting copolymer with fatty amines or alcohols, or a mixture thereof, with a C ₆ -C ₂₈ alkyl length, and as a dispersing component - a bivalent compound obtained by the reaction of multistage functionalization of a rigid framework molecule of adamantane to obtain the final product 1,3,5-trialkylamido-7-aminoadamantane of general formula (II)

where R is selected from hydrocarbon groups containing from 6 to 26 carbon atoms. The depressant-dispersant additive for diesel fuels contains a dispersant component, a depressant component and a solvent in the following ratio of components, wt%:

dispersing component from 3 to 30 depressant component from 35 to 70 solvent from 25 to 60

The solvent can be toluene, xylene, diethylbenzene, extra heavy aromatic solvent, Solvesso 150 or other aromatic solvents.

Implementation of the invention

In this section of the description, the most preferred embodiment of the invention will be given, which, however, does not limit other possible embodiments explicitly following from the materials of the application and understood by a person skilled in the art.

The method of obtaining a depressant-dispersant additive for diesel fuel is carried out in the following most preferred way.

The method of obtaining the declared additive includes 3 stages:

1) Synthesis of the depressant component of the additive based on copolymerization of C ₆ -C ₃₀ alpha-olefin with maleic anhydride, followed by modification with fatty amines or alcohols, or their mixture with a C ₆ -C ₂₈ alkyl length;

2) Synthesis of a dispersant additive component based on the modification of a rigid framework molecule, for example, an adamantane molecule;

3) Receiving DCF. Preparation of the final recipe for DDF. Each stage will be discussed in detail below.

Synthesis of the depressant component

At the first stage of obtaining a depressant component, a radical copolymerization reaction of maleic anhydride and a fraction of C ₆ -C ₃₀ alpha-olefins is carried out with the participation of a radical polymerization initiator at a temperature of 90-140 ° C for 3-5 hours in an appropriate solvent. The reaction proceeds as follows:

where R ₁ is an alkyl radical with the number of carbon atoms C ₄ -C ₂₈ .

As the solvent, for example, toluene, xylene, diethylbenzene, superheavy aromatic solvent, Solvesso 150 or other aromatic solvents can be used.

Tert-butyl peroxybenzoate, dibenzoyl peroxide or azo-bis-isobutyronitrile can be used as the initiator of radical polymerization.

Further, in one embodiment of the claimed invention, to obtain a type 1 depressant component, the previously obtained copolymer of alpha-olefins and maleic anhydride is modified with amines. Depending on the ratio of the starting copolymer and the modifying amine, the reaction can proceed according to the following schemes:

where R ₁ is an alkyl radical with the number of carbon atoms C ₄ -C ₂₈ , and R ₂ is an alkyl radical with the number of carbon atoms C ₄ -C ₃₀ .

The reaction is carried out at a temperature of 90-150 ° C for 2-3 hours with constant stirring.

The amine modifier is any commercially available amine that reacts with such a copolymer, including, but not limited to, primary, secondary and tertiary amines. For example, tallowamine, hydrogenated tallowamine, cocoamine, soyamine, oleylamine, octadecylamine, hexadecylamine, dodecylamine, 2-ethylhexylamine, dicocoamine, ditallovamine, dehydrogenated tallowamine, didecylamine, dioctadecylamine, N-coopoco-1, N-diamino 3-diaminopropane, N, N, N-trimethyl-N-tallow-1,3-diaminopropane, N-oleyl-1,3-diaminopropane, N, N, N-trimethyl-N-9-octadecenyl-1,3- diaminopropane, 3-tallow-1,3-hexahydropyrimidine, and mixtures thereof.

In another embodiment of the invention, a previously obtained copolymer of alpha-olefins and maleic anhydride is modified with alcohols to produce a Type 2 depressant component. The reaction proceeds as follows:

where R ₁ is an alkyl radical with the number of carbon atoms C ₄ -C ₂₈ , R ₃ is an alkyl radical with the number of carbon atoms C ₁ -C ₃₆ .

The reaction is carried out at a temperature of 90-160 ° C for 2-3 hours with constant stirring.

Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, mixtures of C ₁₀ -C ₂₀ alcohols, C ₁₂ -C ₃₆ alcohols of Gerbet, behenyl alcohols and their mixtures are used as alcohols.

In another embodiment, to obtain a type 3 depressant component, the previously obtained copolymer of alpha-olefins and maleic anhydride is modified first with alcohols and then with amines. The reactions are carried out according to the following schemes:

Here, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, mixtures of C ₁₀ -C ₂₀ alcohols, C ₁₂ -C ₃₆ alcohols of Guerbet, behenyl alcohols and their mixtures are also used as alcohols. The amine modifier is any commercially available amine that reacts with such a copolymer, including, but not limited to, primary, secondary and tertiary amines. For example, tallowamine, hydrogenated tallowamine, cocoamine, soyamine, oleylamine, octadecylamine, hexadecylamine, dodecylamine, 2-ethylhexylamine, dicocoamine, ditallovamine, dehydrogenated tallowamine, didecylamine, dioctadecylamine, N-coopoco-1, N-diamino 3-diaminopropane, N, N, N-trimethyl-N-tallow-1,3-diaminopropane, N-oleyl-1,3-diaminopropane, N, N, N-trimethyl-N-9-octadecenyl-1,3- diaminopropane, 3-tallow-1,3-hexahydropyrimidine, and mixtures thereof.

Thus, a depressant component is obtained for preparing a depressant-dispersant additive according to one of the proposed options.

Synthesis of a dispersant component

The dispersing component is obtained by multi-stage modification of the rigid framework structure of the adamantane molecule to obtain a bivalent compound on the adamantane platform, namely, 1,3,5-trialkylamido-7-aminoadamantane.

In a particular embodiment of the invention, the synthesis includes a multistage process including the following steps:

1) Obtaining 1,3,5-triphenyladamantane by interaction with intense boiling of a solution of 1-bromoadamantane and tert-butyl bromide in pre-dried benzene with the addition of aluminum chloride, followed by the addition of the reaction mixture to cold water and the addition of diethyl ether, and by filtering and recrystallizing the precipitated draft. The reaction proceeds as follows:

2) Obtaining 1-bromo-3,5,7-triphenyladamantane by interaction with heating a solution of 1,3,5-triphenyladamantane, tetrabromomethane and tetrabutylammonium bromide in fluorobenzene and 50% sodium hydroxide solution, followed by evaporation of the reaction mass, mixing with water and extraction three portions of dichloromethane, with further evaporation of dichloromethane and recrystallization of the residue from a mixture of hexane / ethyl acetate (at a molar ratio of a mixture of 1: 1). The reaction proceeds as follows:

3) Obtaining 1,3,5-triphenyl-7-acetylaminoadamantane by interaction with heating a suspension of 1-bromo-3,5,7-triphenyladamantane in acetonitrile and concentrated sulfuric acid, followed by evaporation of the reaction mass, adding water and extracting with three portions of ethyl acetate , followed by evaporation of the resulting extract. The reaction proceeds as follows:

4) Obtaining 1,3,5-tricarboxy-7-acetylaminoadamantane by reacting a solution of 1,3,5-triphenyl-7-acetylaminoadamantane and iodic acid in a mixture of carbon tetrachloride / acetonitrile / water (at a molar ratio of the mixture 3: 2: 3) with ruthenium (III) chloride monohydrate at a temperature of 0 ° C, keeping the reaction mixture for about 3 days with constant stirring, followed by adding water and neutralizing the excess oxidation with sodium sulfite, bringing the aqueous layer to pH 1 with 2 N hydrochloric acid and extracting with four portions of ethyl acetate , followed by evaporation of the resulting extract. The reaction proceeds as follows:

5) 1-aminoadamantane-3,5,7-tricarboxylic acid hydrochloride by interaction with heating a suspension of 1,3,5-tricarboxy-7-acetylaminoadamantane in water with concentrated hydrochloric acid, followed by washing the reaction mixture with three portions of ethyl acetate and evaporation of the aqueous part ... The reaction proceeds as follows:

6) 1,3,5-trialkylamido-7-aminoadamantane by reacting with heating under reflux a solution of 1-aminoadamantane-3,5,7-tricarboxy acid hydrochloride in chloroform with thionyl chloride, followed by evaporation of the reaction mixture to dryness, adding to the residue a mixture of chloroform / toluene (at a molar ratio of a mixture of 1: 1) and amines with an alkyl tail length of C ₆ -C ₂₆ and triethylamine, followed by washing with four portions of 25% ammonia solution and two portions of water and evaporation of the organic layer. The reaction proceeds as follows:

where R is an alkyl radical with the number of carbon atoms C ₆ -C ₂₆ .

By varying the length of alkyl radicals in the dispersant molecule, it is possible to achieve effective adsorption on the surface of crystals of paraffins of middle distillates of different composition.

Preparation of the final formulation of the depressant-dispersant additive.

The depressant-dispersant additive includes:

- dispersing component from 3 to 30 wt%,

- a depressant component from 35 to 70 wt%,

- solvent from 25 to 60 wt.%.

As the solvent, for example, toluene, xylene, diethylbenzene, superheavy aromatic solvent, Solvesso 150 or other aromatic solvents can be used.

The method of obtaining a depressant-dispersant additive is illustrated by the examples presented below, but is not limited to them.

Example 1 (prototype RU 2684412)

Obtaining a depressor component.

To a solution of 1.95 g of maleic anhydride, 3.6 g of a mixture of C ₈ -C ₂₄ 1-olefins in 6 ml of toluene at a temperature of 90 ° C, add 0.125 g of a radical polymerization initiator dibenzoyl peroxide and stirring for 23 hours at a temperature of 90 ° C. The reaction mixture is evaporated to obtain a residue of 5.3 g (yield 95 wt%) of the depressant component DP-1.

Getting a dispersing component.

To a solution of 0.46 g of methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, 1.6 g of SCD (ratio 1:10) and 0.25 g of hexene-1 in 10 ml of toluene at a temperature of 70 ° With add a solution (molar ratio 1: 100000 catalyst: olefins) 0.2 mg of diethyl ruthenium metal complex catalyst K1 in 0.1 ml of toluene and stirred at 70 ° C for 8 hours, then the reaction mixture is hydrogenated with hydrogen at a pressure of 10 atm in the presence of palladium, then filtered through alumina and the filtrate is evaporated.

Get 2.2 g (yield 94 wt%) dispersant component of the depressant-dispersant additive DG-1 to diesel fuel.

Obtaining a depressant-dispersant additive.

To a solution of 3 g of a depressant component (DP-1) in 5 ml of toluene is added a solution of 7 g of a dispersing component (DG-1) in 5 ml of toluene. The resulting solution was stirred for 30 min at room temperature, then the toluene was evaporated to obtain 10 g (100 wt% yield) of a depressant-dispersant additive (DDP 1).

Example 2

Obtaining a depressor component.

A solution of 132 g (0.5 mol) of alpha-olefins, for example, "NEODENE 2022", in 120 g of diethylbenzene is heated to 100 ° C and 49 g (0.5 mol) of maleic anhydride and 2 g of tert-butyl peroxybenzoate are added. The temperature of the reaction mass is raised to 130 ° C and kept with stirring for 4 hours. Next, 150 g (0.025 mol of maleic anhydride) of a solution of the obtained copolymer of alpha-olefins and maleic anhydride is heated to 90 ° C and 67.25 g (0.025 mol) of stearylamine are added. The temperature of the reaction mass is raised to 150 ° C and kept for 3 hours with constant stirring.

Getting a dispersing component.

Synthesis of 1,3,5-triphenyladamantane. A solution of 15 g (0.069 mol) of 1-bromoadamantane and 18.9 g (0.138 mol) of tert-butyl bromide in 300 ml of previously dried benzene with the addition of 0.75 g (0.0057 mol) of aluminum chloride is kept for 30 minutes at vigorous boiling. Then the reaction mass is poured into cold water and 100 ml of diethyl ether are added. The formed precipitate was filtered off and recrystallized from benzene. Product yield - 8.1 g.

Synthesis of 1-bromo-3,5,7-triphenyladamantane. To a solution of 8 g (0.022 mol) of 1,3,5-triphenyladamantane, 29.3 g (0.088 mol) of tetrabromomethane and 0.8 g (0.0024 mol) of tetrabutylammonium bromide in 180 ml of fluorobenzene, add 12 ml of 50% sodium hydroxide solution. The reaction mass is heated and kept at 75 ° C for 24 hours. The reaction mass is evaporated, for example, on a rotary evaporator, mixed with water and extracted with three portions of 20 ml of dichloromethane. Then the dichloromethane is evaporated, for example, on a rotary evaporator, the residue is recrystallized from a hexane / ethyl acetate mixture (at a ratio of 1: 1). Product yield - 10.4 g.

Synthesis of 1,3,5-triphenyl-7-acetylaminoadamantane. To a suspension of 10 g (0.0224 mol) of 1-bromo-3,5,7-triphenyladamantane in 300 ml of acetonitrile add 14 ml (0.26 mol) of concentrated sulfuric acid. The reaction mass is kept at boiling for 24 hours. Then the reaction mass is evaporated, for example, on a rotary evaporator, water is added and extracted with three portions of 150 ml of ethyl acetate. The extract obtained is evaporated, for example, on a rotary evaporator. Product yield - 7.6 g.

Synthesis of 1,3,5-tricarboxy-7-acetylaminoadamantane. To a solution of 6.4 g (0.0152 mol) of 1,3,5-triphenyl-7-acetylaminoadamantane and 156 g (0.684 mol) of iodic acid in 350 ml of a mixture of carbon tetrachloride / acetonitrile / water (at a ratio of 3: 2: 3) at 0 ° C, 0.54 g (0.0026 mol) of ruthenium (III) chloride monohydrate is added. The reaction mass is kept for 3 days with constant stirring. Then water is added to the reaction mass and the excess of the oxidizing agent is neutralized with sodium sulfite. The aqueous layer is brought to pH = 1 with 2N hydrochloric acid and extracted with four portions of 100 ml of ethyl acetate. The extract obtained is evaporated, for example, on a rotary evaporator. Product yield - 4 g.

Synthesis of 1-aminoadamantane-3,5,7-tricarboxylic acid hydrochloride. A suspension of 4 g (0.0123 mol) of 1,3,5-tricarboxy-7-acetylaminoadamantane in 60 ml of water with the addition of 15 ml of concentrated hydrochloric acid is boiled for 24 hours. Then the reaction mass is washed with three portions of 30 ml of ethyl acetate. The aqueous portion is evaporated, for example, on a rotary evaporator. The product yield is 3.78.

Synthesis of 1,3,5-trialkylamido-7-aminoadamantane. To a solution of 3.78 g (0.0118 mol) of 1-aminoadamantane-3,5,7-tricarboxy acid hydrochloride in 120 ml of chloroform add 2.2 ml (0.03 mol) of thionyl chloride and the reaction mixture is heated under reflux in within 20 hours. Then the reaction mass is evaporated to dryness, for example, on a rotary evaporator. To the resulting residue are added 40 ml of a mixture of chloroform / toluene (at a ratio of 1: 1) and 9.9 g (0.036 mol) of hydrogenated tallow amines and 5 ml of triethylamine. The reaction mass is heated under reflux at vigorous reflux for 24 hours. Then the reaction mass is washed with four portions of 30 ml of 25% ammonia solution and two portions of 30 ml of water. The organic layer is evaporated, for example, on a rotary evaporator. The product yield is 10.75.

To obtain a depressant-dispersant additive, 70 wt.% Of a depressant component, 3 wt.% Of a dispersant component and 27% wt. aromatic solvent.

To 27 g of toluene add 3 g of a dispersing component at a temperature of 40 ° C and constant stirring. After dissolving the dispersing component in toluene, 70 g of the depressant component preheated to 50 ° C are added. Stirred and get the final product (DDP 2).

Example 3

The depressor component is prepared in a similar manner to that described in Example 2.

The dispersing component is obtained in a similar way described in example 2, only at the last stage when obtaining 1,3,5-trialkylamido-7-aminoadamantane to the resulting residue after evaporation add 40 ml of a mixture of chloroform / toluene (at a ratio of 1: 1) and 6, 84 g (0.036 mol) of primary amines C ₁₀ -C ₁₄ (TU 2413-006-67273753-2013, Amines C ₁₀ -C ₁₄ grade B, URALCHEM) and 5 ml of triethylamine. The reaction mass is also heated under reflux with vigorous boiling for 24 hours. Then the reaction mass is washed with four portions of 30 ml of 25% ammonia solution and two portions of 30 ml of water. The organic layer is evaporated, for example, on a rotary evaporator. The product yield is 7.6 g.

To obtain a depressant-dispersant additive, 65 wt.% Of a depressant component, 10 wt.% Of a dispersant component and 25 wt.% Of an aromatic solvent are taken.

To 25 g of toluene add 10 g of a dispersing component at a temperature of 40 ° C and constant stirring. After dissolving the dispersant component in toluene, 65 g of the depressant component preheated to 50 ° C are added. Stirred and get the final product (DDP 2).

Example 4

Obtaining a depressor component.

A solution of 132 g (0.5 mol) of alpha-olefins, for example, "NEODENE 2022", in 120 g of diethylbenzene is heated to 100 ° C and 49 g (0.5 mol) of maleic anhydride and 2 g of tert-butyl peroxybenzoate are added. The temperature of the reaction mass is raised to 130 ° C and kept with stirring for 4 hours. Next, 150 g (0.025 mol of maleic anhydride) of a solution of the obtained copolymer of alpha-olefins and maleic anhydride is heated to 90 ° C and 81 g (0.025 mol) of a mixture of alcohols, for example, "NAFOL 22+", are added. The temperature of the reaction mass is raised to 160 ° C and kept for 3 hours with constant stirring.

The dispersant component is prepared in a similar manner to that described in example 2.

To obtain a depressant-dispersant additive, 50 wt% of a depressant component, 15 wt% of a dispersant component and 35 wt% of an aromatic solvent are taken.

To 35 g of Solvesso 150 add 15 g of the dispersing component at 40 ° C and constant stirring. After dissolving the dispersing component in toluene, add 50 g of the depressant component preheated to 50 ° C. Stirred to give the final product (DDP 4).

Example 5

The depressor component is prepared in a similar manner to that described in Example 4.

The dispersant component is prepared in a similar manner to that described in example 3.

To obtain a depressant-dispersant additive, 35 wt% of a depressant component, 30 wt% of a dispersant component and 35 wt% of an aromatic solvent are taken.

To 35 g of xylene add 30 g of a dispersing component at a temperature of 40 ° C and constant stirring. After dissolving the dispersing component in toluene, 35 g of the depressant component preheated to 50 ° C are added. Stirred and get the final product (DDP 5).

Example 6

Obtaining a depressor component.

A solution of 132 g (0.5 mol) of alpha-olefins, for example, "NEODENE 2022", in 120 g of diethylbenzole is heated to 100 ° C and 49 g (0.5 mol) of maleic anhydride and 2 g of tert-butyl peroxybenzoate are added. The temperature of the reaction mass is raised to 130 ° C and kept with stirring for 4 hours. Next, 150 g (0.025 mol of maleic anhydride) of a solution of the obtained copolymer of alpha-olefins and maleic anhydride is heated to 90 ° C and 81 g (0.025 mol) of a mixture of alcohols, for example, "NAFOL 22+", are added. The temperature of the reaction mass is raised to 140 ° C and kept for 2 hours with constant stirring, then the reaction mass is cooled to 90 ° C and 67.25 g (0.025 mol) of stearylamine are added. The temperature of the reaction mass is raised to 150 ° C and kept for 3 hours with constant stirring.

The dispersant component is prepared in a similar manner to that described in example 2.

To obtain a depressant-dispersant additive, 35 wt.% Of a depressant component, 5 wt.% Of a dispersant component and 60 wt.% Of an aromatic solvent are taken.

To 60 g of toluene add 5 g of a dispersing component at a temperature of 40 ° C and constant stirring. After dissolving the dispersing component in toluene, 35 g of the depressant component preheated to 50 ° C are added. Stirred and get the final product (DDP 6).

Example 7

The depressor component is prepared in a similar manner to that described in Example 6.

The dispersant component is prepared in a similar manner to that described in example 3.

To obtain a depressant-dispersant additive, take 57 wt.% Of a depressant component, 3% wt. dispersing component and 40% wt. aromatic solvent.

To 40 g of nefras add 3 g of a dispersing component at a temperature of 40 ° C and constant stirring. After dissolving the dispersing component in toluene, 57 g of the depressant component preheated to 50 ° C are added. Stirred to give the final product (DDP 7).

To determine sedimentation stability, diesel fuel with a depressant-dispersant additive was kept in accordance with the method of STO 11605031-041-2010 JSC VNII NP for 16 hours at a temperature of 5 ° C below the cloud point temperature, then the maximum filterability temperature was determined 20 % upper and 20% lower fuel layers. The data obtained are shown in Table 1.

Several base diesel fuels produced by various refineries of the Russian Federation were selected for testing.

Thus, as follows from the presented examples and the table, it can be concluded that the introduction of the claimed depressant-dispersant additive into diesel fuel leads to a decrease in the maximum filterability temperature of diesel fuel by 20-27 ° C, and also provides sedimentation stability during its cold storage. ...

Claims (9)

1. A depressant-dispersant additive for diesel fuels containing a mixture of a depressant and a dispersant component in a solvent, in which a modified copolymer of maleic anhydride and alpha-olefins of general formula (I) is used as a depressant component

where R _{1 is} selected from hydrocarbon groups containing from 6 to 30 carbon atoms, and X and Y can be hydroxyls and (or) residues from amines or alcohols, or a mixture thereof, with the length of the alkyl radical C6-C28, obtained by the reaction of radical copolymerization of maleic anhydride and a fraction of alpha-olefins C6-C30 with the participation of a radical polymerization initiator in an appropriate solvent, and the subsequent modification of the resulting copolymer with fatty amines or alcohols, or a mixture thereof, with an alkyl length of C6-C28, characterized in that as a dispersing component it contains a bivalent compound obtained by the reaction of multistage functionalization of a rigid framework molecule of adamantane to obtain the final product of 1,3,5-trialkylamido-7-aminoadamantane of general formula (II)

where R is selected from hydrocarbon groups containing from 6 to 26 carbon atoms, with the following ratio of components, wt%: dispersing component from 3 to 30 depressant component from 35 to 70 solvent from 25 to 60 2. The depressant-dispersant diesel fuel additive according to claim 1, wherein the solvent is toluene, xylene, diethylbenzene, extra heavy aromatic solvent, Solvesso 150 or other aromatic solvents.