RU2619124C1 - Method of obtaining anti-turbulent additive, method of milling polyalphaolefin for it and anti-turbulent additive - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of obtaining the anti-turbulent additive includes (co) polymerisation of polyolefin in bulk, possibly pre-grinding, cryogenic grinding, heating the mixture to room temperature, introducing an anti-agglomerator into polyalphaolefin before preparing a suspension, mixing grinded polyalphaolefin particles with suspending liquid to form the suspension. As an anti-agglomerator, a copolymer of vinyl acetate and ethylene is taken with vinyl acetate content of 26-40% in the anti-agglomerator copolymer. The anti-agglomerator is introduced during the cryogenic grinding of polyalphaolefin, or during its preliminary and cryogenic grinding, or during cryogenic grinding and immediately after cryogenic grinding, or during the pre-grinding, or during cryogenic grinding and after cryogenic grinding. The total amount of anti-agglomerator is 5-80% by weight of the polyalphaolefin.

EFFECT: dissolution of antiagglomerator in hydrocarbons, including at low temperatures, exclusion of polyalphaolefin agglomeration and therefore elimination of "cold flow" effect of polyalphaolefin over a wide range of ambient temperatures, including at elevated temperatures, and elimination of co-crystallization of antiagglomerator with paraffins at low temperatures.

7 cl, 5 ex

Description

The invention relates to the petrochemical and chemical industries, in particular to the production of anti-turbulent additives that reduce the hydrodynamic resistance in pipelines for transporting oil and oil products, hydrocarbon fuels. The invention can also be used for grinding amorphous polymers that do not have a crystal lattice - elastomers, for example rubbers.

The use of (co) polymers of higher alpha olefins to reduce the hydrodynamic resistance of a hydrocarbon stream flowing in a pipeline is known. Such drag reducing agents, anti-turbulent additives, are mainly used in the form of suspensions and are suspension type additives.

Suspension anti-turbulent additives are known [Bulletin of the Tomsk Polytechnic University. 2006.V. 309. Number 3. from. 112-115; G.V. Nesyn, Yu.V. Suleimanova et al. Antiturbulent additive of suspension type based on higher α-olefins, as well as US 4837249, 06/06/1989; US 4826728, 05/02/1989]. Their preparation includes the polymerization of higher α-olefins in bulk, then the resulting polymer is ground at cryogenic temperatures and a suspension of the ground polymer is prepared in an aqueous or non-aqueous medium. The method of cryogenic grinding of the polymer described in these sources is usually difficult due to the amorphous state of the polymer, which is prone to adhesion of particles with each other over time after grinding. This process is called "cold flow." In cold weather, polymer agglomerates are formed that prevent its use as an additive. Repeated grinding of the polymer leads to the loss of molecular weight, which significantly reduces its effectiveness. To prevent such a process, anti-agglomerators are used - separating agents that coat polymer particles and prevent their agglomeration both in dry form and in suspension.

Organic and inorganic substances can be used as anti-agglomerators. Organic anti-agglomerators are known: organic fatty acids - oleic acid, linoleic acid, stearic acid, palmitic acid (US Patent No. 6774094). Also used are salts of fatty organic acids, acid amides - stearic acid amide, ethylene bis stearamide (US Patent No. 6172151), esters of fatty organic acids. Polymeric materials are also used as organic anti-agglomerators: polyethylene, polypropylene (US application No. 20110105642), polystyrene, polyphenyl sulfide, polyethylene terephthalate, polyethylene waxes, polyamide, polyphenylene oxide, polyvinyl chloride, etc. Talc, silica are used as inorganic anti-agglomerators, silica, alumina, oxides, carbonates, sulfates, phosphates of magnesium, calcium and barium. The use of calcium stearate as an anti-agglomerator is known (US Patent No. 5,504,131).

In the patent of the Russian Federation 2303606 "Ultra-high molecular weight polyolefin used as an additive that improves the fluidity of cold liquids", IPC C08F 10/10, C08F 10/14, C10L 1/10, C10L 1/16, publ. 07/27/2007, methods for producing an anti-turbulent additive using polymerization are described, including: copolymerization of vinyl aromatic monomer (styrene) with higher alpha-olefins (hexene, octene, decene, dodecene, tetradecene) on a catalytic system titanium trichloride + diisobutyl chloride in bulk from a polymer subsequent drying in vacuo from unreacted monomers, and subsequent cryogenic grinding of polyalphaolefin; preparation of a suspension of a hydrodynamic drag reducing agent. For this, small polymer particles are mixed with a suspending liquid in a mixing vessel to form a mixture of a suspending liquid and polymer particles. A suspending liquid is any liquid that is a non-solvent for an ultra high molecular weight polymer. The most commonly used water. For many other mixtures, lower alcohols such as methanol, ethanol, or mixtures thereof, can be used as suspending liquid. Other components may be added to the suspension before, during, or after mixing the crushed polymer particles with the suspending liquid in order to facilitate the formation of the suspension and / or preservation of the suspension. To facilitate the preservation of the suspension of non-sticky ultra-high molecular weight polymer particles, a suspension stabilizer is introduced. Typical suspension stabilizers are anti-agglomerators: talc, tricalcium phosphate, magnesium stearate, silicon dioxide, polyanhydride polymers, sterically hindered alkyl phenol antioxidants, amide waxes such as stearamide, ethylene bis stearamide and oleamide, graphite. The number of injected stabilizer suspension may be in the range from 0 to 40% of the mass. suspending liquid, but preferably in the range of 5-25 wt. -%, and most preferably 8-12% of the mass.

From the patent of the Russian Federation 2303606 there is also known a method of grinding the obtained polyalphaolefin, carried out before preparing the suspension of the anti-turbulent additive, according to which it is crushed in two stages. The first stage is the preliminary grinding of polyalphaolefin in a coarse mill to pieces of diameter 1.4-1.5 cm at ambient temperature. Large grinding can be carried out with preliminary cooling of the polyalphaolefin, for example, by spraying liquid nitrogen, to a temperature of from -10 ° C to -100 ° C. In the second stage, the crushed pieces of polyalphaolefin are pre-cooled to its glass transition temperature from about -130 to -150 ° C, for example, in a closed screw conveyor with nozzles for spraying liquid refrigerant. The cooled polyalphaolefin particles are transported to a cryogenic mill, in which its glass transition temperature is maintained or lower. In this mill, hammer or friction, polyalphaolefin is crushed to small particles with a diameter of 10-800 microns. Next, the crushed particles of polyalphaolefin are subjected to separation, for example, using rotating or vibrating screens, to remove evaporating refrigerant and sort the crushed particles by size. Larger pieces are returned for cooling and regrind, and particles of about 400 microns in size are sent to form a suspension of an anti-turbulent additive.

The analogue described above is selected as the closest.

A disadvantage of the closest analogue is the use of one or more of the above substances as an anti-agglomerator, which are not soluble in oil, oil products, gas condensate, in a wide fraction of light hydrocarbons and cannot act as an agent that reduces resistance. They have no other function besides the function of the separating agent; they are polluting components for the anti-turbulent additive agents they process. As indicated in the closest analogue, the amount of suspension stabilizer should be minimized or eliminated, where possible, to reduce the amount of material in the suspension, which does not act as an agent that reduces the resistance of the medium.

In addition, the calcium stearate used as an anti-agglomerator is a calcium salt of stearic acid of the general formula Ca (C ₁₇ H ₃₅ COO) ₂ . Being a solid substance in the composition of the commodity additive, insoluble in oil and oil products, it will be released in the stagnant zones of pipelines, when fuel is stored in containers, in tanks and accumulate over time in the form of additional bottom sediments. This creates a problem for the consumer and additional costs for cleaning technological tanks.

Another problem associated with calcium stearate is that when cooling oil, oil product or another hydrocarbon, it will form complexes with paraffins, becoming in this case the center of co-crystallization, which in turn reduces the low-temperature performance of oil and hydrocarbon fuels, which limits geographical areas of their application.

The disadvantage of the method of grinding polyalphaolefin is the following.

At the first stage of grinding, it is difficult to achieve the sizes of a polyalphaolefin with a diameter of 1.4-1.5 cm at ambient temperature. The crushed particles stick together, forming larger agglomerates. To achieve such a result as in the prototype, it is necessary to pre-cool the pieces of polyalphaolefin and to carry out the grinding process for a long time. The grinding process is time-consuming and energy-consuming for the operation of the grinder, and for pre-cooling pieces of polyalphaolefin, and with a repeated cycle of cooling and grinding sorted large pieces. At the same time, the result of grinding is ambiguous, it is necessary to return pieces to repeated preliminary grinding.

The objective of the invention is to eliminate pollution of the flow of hydrocarbons, the deposition of anti-agglomerator in the stagnant zones of pipelines, the exclusion of bottom sediments in tanks for storage and transportation of petroleum products.

Another objective is to expand the operating temperature range of anti-turbulent additives.

The objective is also to simplify the grinding of polyalphaolefin and reduce the cost of grinding.

The technical result is the possibility of dissolution of the anti-agglomerator in hydrocarbons, including at low temperatures, the exclusion of agglomeration of polyalphaolefin (PAO), and therefore the exclusion of the effect of the "cold flow" of PAO in a wide range of ambient temperatures, including at elevated temperatures for its use, exclusion co-crystallization of the anti-agglomerator with paraffins at low temperatures.

The problem is solved and the technical result is realized by the method of obtaining anti-turbulent additives, including:

- (Co) polymerization of PAO in bulk,

- PAO grinding, including its grinding at a temperature below its glass transition temperature - cryogenic grinding, for which it is mixed with liquid nitrogen,

- Heating the mixture to room temperature to remove nitrogen,

- Introduction to the PAO anti-agglomerator before preparing the suspension, in order to avoid adhesion of the particles of PAO to each other,

- Mixing the crushed particles of PAO with a suspending liquid, as in analogues, with water, lower alcohols (methanol, ethanol) or their mixtures, with the formation of a suspension.

The difference between the invention and the prototype is the use of a vinyl acetate-ethylene copolymer as an anti-agglomerator with a vinyl acetate content in the anti-agglomerator copolymer of 26-40%, while the resulting suspension contains components in the following ratio, mass. %:

Polyalphaolefin 25-40 Antiagglomerator 7-20 Suspending Fluid Rest

and the anti-agglomerator is introduced during cryogenic grinding of PAO, or during preliminary and cryogenic grinding, or during its cryogenic grinding, and immediately after cryogenic grinding, or during preliminary grinding, and cryogenic grinding, and after cryogenic grinding, and when the anti-agglomerator is introduced during preliminary grinding, its amount is 5-10% by weight of the PAO, and with the introduction of the anti-agglomerator after grinding the PAO, the amount of the introduced anti-agglomerator is up to 30% by weight of the polymer.

The problem is also solved by the method of grinding polyalphaolefin as an amorphous polymer, in accordance with which its grinding is carried out in stages. One coarse grinding step, if necessary, is carried out in a coarse grinding mill at ambient temperature. In a subsequent cryogenic grinding step, the crushed pieces of polyalphaolefin are pre-cooled to a temperature below its glass transition temperature. The chilled pieces of PAO are subjected to cryogenic grinding to fine particles with a diameter of 400-500 microns with their subsequent separation.

The difference between the present invention and the prototype is the use of an anti-agglomerator in the form of a vinyl acetate-ethylene copolymer with a vinyl acetate content in the anti-agglomerator copolymer of 26-40%, coarse grinding, if necessary, to particles of size (4 ÷ 7) × (4 ÷ 7) cm, preliminary grinding of the polyalphaolefin to pieces from 5 × 5 mm to 6x6 mm in size after the coarse grinding operation and before cryogenic grinding, at the cryogenic grinding stage of the polyalphaolefin, an anti-agglomerator cooled to the glass transition temperature is added to it polyalphaolefin, either with preliminary and cryogenic grinding of PAO, or with its cryogenic grinding and immediately after cryogenic grinding, or with preliminary grinding of PAO, and cryogenic grinding, and after cryogenic grinding, and when the anti-agglomerator is introduced during preliminary grinding, its amount is 5- 10% by weight of PAO, with the introduction of the anti-agglomerator after grinding the PAO, the amount of introduced anti-agglomerator is up to 30% by weight of the polymer, and the total amount of anti-agglomerator it is 5-80% by weight of the PAO.

PAO grinding can be carried out with the addition of a pre-finely ground anti-agglomerator to a size of 50-150 μm, or the anti-agglomerator can be grinding together with PAO grinding, for which the anti-agglomerator is placed in a cooling chamber to the glass transition temperature of the PAO, after which both components are ground together to a PAO particle size of 400-500 microns.

The problem is also solved by the composition of the anti-turbulent additive, including polyalphaolefin, suspending liquid, anti-agglomerator, which differs from the prototype in that a vinyl acetate-ethylene copolymer with a content of vinyl acetate in the anti-agglomerator polymer of 26-40% is taken in the following ratio, mass. %:

Polyalphaolefin 25-40 Antiagglomerator 7-20 Suspending Fluid Rest

The mechanism of action of ethylene vinyl acetate copolymers as agents that lower the pour point of oil and oil products, such as diesel fuel, is widely known: the effect is reduced to their effect on the crystallization and structure formation processes of paraffinic, primarily solid hydrocarbons. The most common ideas are about adsorption of additives on paraffin crystals, about the joint crystallization of depressants with additive molecules, and about the possible interaction of additives with solid hydrocarbons with the formation of associated complexes, i.e. the copolymer has a surface effect on paraffin crystals, due to this, from a large spatial structure, paraffin crystals turn into needle-like ones, and the size of crystallizing particles decreases. Information on the use of a copolymer of vinyl acetate with ethylene as a depressant additive for diesel fuel is known from the information from the website autosteam.ru/helpful-info/1190-sopolimery-etilena-s-vinilatsetatom. Due to this effect, the pour point is reduced, dynamic viscosity is reduced, and the fluidity of the oil is improved. At this site, a copolymer with a quantity of vinyl acetate in it with 16% is used to cool the fuel.

The proposed anti-agglomerator was selected in order to avoid subsequent agglomeration of particles of cryogenically ground PAO with each other both in dry form and in commercial form, especially at elevated temperatures (40-50 ° C). The prior art anti-agglomerator selected by the authors is unknown. The result of its use is also unknown.

Due to the absence of negative influence of vinyl acetate-ethylene copolymers on oil refining processes, it is possible to increase the content of anti-agglomerator in the additive to 80% by weight of PAO, the additive acts as a depressant without negative impact on the formation of sediment and other processes.

The copolymer proposed for use as an anti-agglomerator is, like PAO, amorphous, therefore it must also be crushed at temperatures below its glass transition temperature, i.e. in liquid nitrogen using cryomills.

The method is as follows.

The polymer obtained by the polymerization of higher C ₆ -C ₁₂ alpha-olefins is maintained to a high degree of conversion, preferably 90-95%. Then it is subjected to coarse grinding by hand or in a coarse mill to pieces of size (4 ÷ 7) × (4 ÷ 7) cm at ambient temperature. Then, after coarse grinding, PAO is subjected to preliminary grinding to pieces from 5 × 5 mm to 6 × 6 mm in size at ambient temperature on a PM-250 type crusher.

PAO thus ground in order to prevent particles from sticking together is sprinkled with a ground cryogenic method to a size of 50-150 microns with an anti-agglomerator.

PAO prepared in such a way for cryogenic grinding is placed in a chamber with liquid nitrogen, cooled to a glass transition temperature of 20-25 minutes, and then PAO sprayed with crushed anti-agglomerator is crushed to particles with a size of 400-500 microns. At the cryogenic grinding stage of the PAO, the anti-agglomerator can be added directly to the cryomill to the PAO, where both components are cooled to the glass transition temperature of the polyalphaolefin, after which both components are crushed together to a particle size of 400-500 μm. The anti-agglomerator can be added immediately after cryogenic grinding of the PAO, before the preparation of the additive.

To analyze the solubility of the anti-agglomerator in hydrocarbons and the formation of bottom sediments in the stagnant zones of pipelines, sediment formation was assessed by determining the distribution of the additive in the hydrocarbon fraction along the layer height depending on the shelf life of the product at a temperature of + 20 ° С. The settling time reached 30 days.

To assess the presence of agglomeration, caking of a mixture of a vinyl acetate-ethylene copolymer with PAO was studied at high temperatures, placing a sample of the mixture at a temperature of 50 ° С under a load corresponding to a pressure of 0.04 MPa and keeping the sample for a day under the indicated conditions.

Depressor properties of the additive were determined by the filterability coefficient according to GOST 19006-73; filterability limit temperature in accordance with EN 116: 1997; pour point and fluidity - according to GOST 20287-91.

Example 1 - the prototype

1. The grinding of polyalphaolefin was carried out in two stages. The first stage consisted of grinding polyalphaolefin in a coarse mill to pieces of diameter 1.5 cm at ambient temperature. At the second stage, the crushed large pieces of polyalphaolefin were pre-cooled to its glass transition temperature and milled in a cryogenic mill, in which its glass transition temperature was maintained or lower. In this mill, the polyalphaolefin was ground to fine particles with a diameter of 400-500 microns. The cryogenically ground polyalphaolefin was mixed with an anti-agglomerator - calcium stearate, taken in an amount of 40% by weight of the polymer (25% PAO + 10% anti-agglomerator + up to 100% additive medium).

The assessment of the formation of sediment was determined by the distribution of the mixture in the hydrocarbon fraction (nefras) along the height of the layer depending on the shelf life of the product at a temperature of + 20 ° C. The settling time reached 30 days.

For analysis, a polymer crumb solution was prepared with an anti-agglomerator concentration of 0.1% wt. in nephras in the amount of 1000 ml, using mechanical stirring. With fully dissolved polyalphaolefin, the latter was mechanically degraded using a mixer for 1 minute at maximum speed. The resulting mixture was placed in a cylinder with a volume of 1000 cm ³ with a ground stopper, the stopper was tightly closed, the cylinder was left alone. Every 5 days, the samples were subjected to visual inspection to determine the presence of sediment.

After 30 days of storage of the sample during visual inspection, stratification is observed along the height of the nephras volume in the cylinder: there is a transparent layer on top, and a white sediment layer on the bottom. The presence of suspensions was noted immediately after preparation of the solution from polymer chips with the used anti-agglomerator.

2. To assess the caking behavior, characterizing the presence of the agglomeration process, polymer chips with a size of 400-500 microns were mixed with an anti-agglomerator in an amount of 10% by weight of the polymer. 80 g of a mixture of polymer crumb and anti-agglomerator were placed in a mold, a load of 4 kg was placed on top, which provided a load of 0.04 MPa, and was kept at a temperature of + 50 ° C for 4 hours. Allowed to cool, then the mixture was removed polyalphaolefin and stearate from the mold, checked for "cold flow", slightly pressing on the sample by hand. The crumbling mixture was sieved through a sieve with a mesh size of 0.5 μm, determining the number of particles of the original size. The amount of sieved polymer mixture was 85%.

3. Depressor properties of the additive:

The limiting filterability temperature (PTF) and cloud point (Tp) were determined according to GOST 22254;

The pour point (Tg) was determined according to GOST 20287-91.

400-500 microns polymer chips were mixed with an anti-agglomerator in an amount of 10% by weight of the polymer. An initial 0.1% solution of a mixture of polymer chips and an anti-agglomerator using Arctic diesel fuel EURO class 4 type III was prepared.

When dosing additives 20 g / t received the following results:

The PTF of the base fuel without additives was minus 39 ° C; with additive - minus 39 ° С;

TP base fuel without additives was minus 37 ° C; with additive - minus 37 ° С;

Tg of base fuel without additives was minus 47 ° C; with additive - minus 47 ° С.

Example 2

The C ₆ -C ₁₂ higher alpha-olefins were copolymerized on a catalytic system with titanium trichloride and diethylaluminium chloride, the polymerizate was kept to a high degree of conversion (over 85%) in a film made from a copolymer of vinyl acetate and ethylene. The obtained polyalphaolefin was subjected to coarse grinding in a coarse grinding mill at room temperature to particle sizes of 5 × 5 cm, then preliminary grinding was performed on a RM-250 type crusher to particles of size (5 ÷ 6) × (5 ÷ 6) mm. To prevent particles from sticking together, the polyalphaolefin thus ground was poured with a pre-crushed cryogenic method to a size of 50-150 μm by an anti-agglomerator - a copolymer of vinyl acetate and ethylene in an amount of 28% by weight of the polyalphaolefin (the amount of vinyl acetate in the anti-agglomerator is 26%). Thus prepared for cryogenic grinding, the polyalphaolefin was placed in a chamber with liquid nitrogen, allowed to cool to a glass transition temperature of 20-25 minutes, after which the polyalphaolefin with anti-agglomerator was crushed to particles of 400-500 μm in size (polyalphaolefin: anti-agglomerator ratio = 3.6: 1; 25 % PAO + 7.0% anti-agglomerator + up to 100% additive environment).

1. The assessment of the formation of sediment was determined analogously to example 1.

After 30 days of storage of the sample during visual inspection of the precipitation was not observed, the presence of any traces of suspensions was not found.

2. Caking was determined analogously to example 1. When exposed to external forces, the polymer crumbled into particles of their original size in the amount of 93%. The determination was carried out by sieving the polymer through a sieve with a mesh size of 0.5 μm.

3. The depressor properties of the polymer mixture were determined analogously to example 1 at a dosage of additives of 20 g per ton of diesel fuel. The dosage of the anti-agglomerator in this case is 1.4 g per ton of diesel fuel.

PTF base fuel without additives minus 39 ° C; with additive minus 40 ° С;

TP base fuel without additives minus 37 ° C; with additive minus 37 ° С;

Tz base fuel without additives minus 50 ° C; with additive minus 51 ° С.

Example 3

The processes were carried out analogously to example 2, but with the difference that coarse grinding of PAO was not carried out due to its receipt for processing in the form that was already crushed to pieces 5 × 5 cm. A vinyl acetate-ethylene copolymer with an amount of vinyl acetate units in the composition of the copolymer of 30% was taken as an anti-agglomerator. The ratio of polymer alpha-olefin: anti-agglomerator was 2: 1 (50% anti-agglomerator by weight of poly-alpha olefin; 30% PAO and 15% anti-agglomerator + up to 100% additive environment). The addition of the anti-agglomerator was carried out in 2 stages: the anti-agglomerator crushed to a size of 50-150 μm in the amount of 5% by weight of the polyalphaolefin was added by grinding in a RM-250 type grinder at room temperature, the remaining 45% was added by cryogenic grinding.

1. Analysis for the determination of sediment was carried out analogously to example 1. After 30 days of storage of the sample during visual inspection of precipitation was not observed, the presence of any traces of additives or suspensions were not found.

2. The analysis to determine the caking of the polymer mixture was carried out analogously to example 1. The number of sifted polymer mixture was 96%.

3. The determination of indicators of the depressant properties of the additive was carried out analogously to example 1 at a dosage of additives of 20 g per ton of diesel fuel. The dosage of the anti-agglomerator in this case is 3.0 g per ton of diesel fuel.

The PTF of the base fuel without additives was minus 39 ° C; with additive minus 43 ° С;

TP base fuel without additives minus 37 ° C; with additive minus 37 ° С;

Tz base fuel without additives minus 50 ° C; with additive minus 54 ° С.

Example 4

The processes were carried out analogously to example 3, with the difference that the addition of the anti-agglomerator to the polyalphaolefin was carried out in 3 stages: the anti-agglomerator crushed to a size of 50-150 μm in an amount of 10% by weight of PAO was added by grinding in a RM-250 type grinder at room temperature; during cryogenic grinding of PAO, another 40% of anti-agglomerator was added, the remaining 30% of anti-agglomerator with a particle size of 50-150 μm was added after cryogenic grinding of PAO.

The final amount of the anti-agglomerator was 80% by weight of the polyalphaolefin (polyalphaolefin: anti-agglomerator ratio = 1.25: 1; 25% PAO + 20% anti-agglomerator + additive medium up to 100%, the amount of vinyl acetate in the anti-agglomerator is 40%).

Definition of indicators by p.p. 1, 2 and 3 were carried out similarly to the processes described in example 1.

1. The formation of sediment was not observed.

2. The amount of sifted PAO was 98%.

3. Depressor characteristics of the mixture:

At a dosage of additives of 20 g per ton of diesel fuel. The dosage of the anti-agglomerator in this case is 4.0 g per ton of diesel fuel.

PTF base fuel without additives minus 39 ° C; with additive minus 45 ° С;

TP base fuel without additives minus 37 ° C; with additive minus 37 ° С;

Tz base fuel without additives minus 50 ° C; with additive minus 56 ° С.

Example 5

The processes were carried out analogously to example 3, with the difference that the addition of the anti-agglomerator to the polyalphaolefin was carried out with simultaneous cryogenic grinding of the PAO and the anti-agglomerator, taken in an amount of 25% by weight of the PAO.

The ratio of polyalphaolefin: anti-agglomerator was 4: 1; 40% PAO + 10% anti-agglomerator + additive environment up to 100%, the amount of vinyl acetate in the anti-agglomerator 40%.

Definition of indicators by p.p. 1, 2 and 3 were carried out similarly to the processes described in example 1.

1. No precipitate was observed.

2. The amount of sieved polymer was 94%.

3. Depressor characteristics of the mixture:

At a dosage of additives of 20 g per ton of diesel fuel. The dosage of the anti-agglomerator in this case is 1.0 g per ton of diesel fuel.

PTF base fuel without additives minus 39 ° C; with additive minus 40 ° С;

TP base fuel without additives minus 37 ° C; with additive minus 37 ° С;

Tz base fuel without additives minus 50 ° C; with additive minus 51 ° С.

Thus, the use of the proposed solutions makes it possible to ensure the solubility of the anti-agglomerator in hydrocarbons and to exclude the formation of bottom deposits in stagnant zones of pipelines, to exclude the agglomeration of additive particles at high temperatures, at least up to plus 50 ° С, to achieve depressant properties of the additive, excluding its co-crystallization with paraffins. The latter circumstance is proved by the fact that the turbidity of the fuel occurs due to the precipitation of paraffin crystals, while the cloud point indirectly indicates the severity of the paraffins present. The higher the cloud point, the more fusible paraffins are present in the fuel. It is important that the cloud point does not get worse when using additives. Studies have found that in the proposed solutions, the pour point (crystallization), when the fuel stops flowing due to paraffins, is lower than the pour point of the mixture in the prototype.

In the prototype, coarse grinding preferably takes place at 5-15 ° C. To do this, liquid refrigerant is sprayed inside the chamber. Using the invention allows this step to be carried out at an ambient temperature between 20 and 25 ° C.

Claims (10)

1. A method of producing an anti-turbulent additive, comprising (co) polymerizing a polyalphaolefin in bulk, possibly pre-grinding, cryogenic grinding, heating the mixture to room temperature, introducing an anti-agglomerator into a polyalphaolefin before preparing a suspension, mixing the ground polyalphaolefin particles with a suspending liquid to form a suspension, characterized in that a vinyl acetate-ethylene copolymer with a vinyl acetate content in the anti-agglomerator copolymer is taken as an anti-agglomerator 26-40%, while the resulting suspension contains components in the following ratio, wt.%: Polyalphaolefin 25-40 Antiagglomerator 7-20 Suspending Fluid Rest and the anti-agglomerator is introduced during cryogenic grinding of the polyalphaolefin, or during preliminary and cryogenic grinding of the polyalphaolefin, or during its cryogenic grinding and immediately after cryogenic grinding, or during its preliminary grinding, during cryogenic grinding and after cryogenic grinding. 2. The method of grinding polyalphaolefin - an amorphous polymer to obtain the anti-turbulent additive according to claim 1, according to which, at the stage of cryogenic grinding, pieces of polyalphaolefin are pre-cooled to a temperature below its glass transition temperature and subjected to cryogenic grinding to particles with a diameter of 400-500 microns with subsequent separation characterized in that prior to cryogenic grinding, the polyalphaolefin is pre-milled to pieces from 5 × 5 mm to 6 × 6 mm in size, at the cryogenic grinding of polyalpha efina, an anti-agglomerator is added to it in the form of a vinyl acetate-ethylene copolymer with a vinyl acetate content in the anti-agglomerator copolymer of 26-40%, or the anti-agglomerator is added during the preliminary and cryogenic grinding of the polyalphaolefin, or during its cryogenic grinding and immediately after cryogenic grinding, or during its preliminary grinding, cryogenic grinding and after cryogenic grinding, and the total amount of anti-agglomerator is 5-80% by weight of polyalphaolefin. 3. The method according to p. 2, characterized in that prior to grinding, a coarse grinding of the polyalphaolefin is carried out to a particle size of (4 ÷ 7) × (4 ÷ 7) cm at ambient temperature. 4. The method according to p. 2, characterized in that when the anti-agglomerator is introduced during preliminary grinding, its amount is 5-10% by weight of the polyalphaolefin. 5. The method according to p. 2, characterized in that when the introduction of the anti-agglomerator after grinding the polyalphaolefin, the amount of the introduced anti-agglomerator is up to 30% by weight of the polyalphaolefin. 6. The method according to p. 2, characterized in that the anti-agglomerator is ground together with a polyalphaolefin. 7. An anti-turbulent additive comprising a polyalphaolefin, a suspending liquid, an anti-agglomerator, characterized in that a vinyl acetate-ethylene copolymer with a content of vinyl acetate in the anti-agglomerator polymer of 26-40% is taken as an anti-agglomerator, in the following ratio, wt.%: Polyalphaolefin 25-40 Antiagglomerator 7-20 Suspending Fluid Rest