Field of the Invention

[0001] The invention relates to drag reducing agents used in case of transportation of petroleum products, in particular, to solid polyacrylate additives.

Background

[0002] There are plasticized latex formulations for improved pumpability (US9644161B2, publ. on 2015-10-15). The solution discloses that hydrocarbon streams, such as crude oil streams, may have reduced drag when an effective amount to reduce the drag of a drag reducing composition is added to a liquid hydrocarbon, where the drag reducing composition includes a drag reducing latex comprising at least one plasticizer in an amount effective to improve the ability to pump the latex into a hydrocarbon composition Latex formulations are known to cause agglomerated particles during pumping operations, and the agglomerated hard particles tend to plug check valves in injection pump equipment, but the inclusion of at least one plasticizer reduces or prevents such problems.

[0003] This hydrocarbon composition having reduced drag comprising: a liquid hydrocarbon selected from the group consisting of crude oil, heavy oil, gasoline, diesel fuel, fuel oil, asphalt, and mixtures thereof; and an effective amount of a drag reducing composition to reduce the drag of the liquid hydrocarbon, where the drag reducing composition comprising: a drag reducing latex comprising: a polymer having at least one monomer selected from the group consisting of acrylates, methacrylates, 2-Ethylhexyl methacrylate, isobutyl methacrylate, butyl methacrylate, 2- Ethylhexyl acrylate, isobutyl acrylate, butyl acrylate, Cl to C6 alcohol esters of acrylic acid or methacrylic acid, styrene, acrylic acid, and combinations thereof; at least one plasticizer in an amount effective to improve the ability to pump the drag reducing latex into the liquid hydrocarbon, where the weight ratio of the at least one plasticizer to drag reducing latex ranges from about 1/99 to about 10/90; and at least one polyether amine.

[0004] However, this solution discloses a latex drag reducing agent (DRA), which is a liquid, not a solid. Therefore, the percentage of the polymeric flow improvers is low in the formulation; in case of storage of the latex composition, take actions to retain its properties, prevent cream formation, etc. [0005] There are non-crystalline, hydrocarbon soluble polymeric flow improvers (US4693321A, publ. on 1987-09-15), which flow improvers are encapsulated to form free- flowing particles comprising normally non-crystalline, hydrocarbon soluble polymers, which have a molecular weight above 1 x 106. Polyalphaolefins are used as improvers; the ureaformaldehyde resin is used as an encapsulant.

[0006] However, polyalphaolefins are used as the polymer in this solution, which cannot be used in heavy oil.

[0007] There is a particulate compound for modifying a characteristic of a fluid (US6841593B2, publ. on 2003-01-16), comprising: a core comprising the compound selected from the group consisting of: polymers formed within a shell; monomers which are polymerized within the shell, where the shell is inert to monomer polymerization; and the shell encapsulating the core, where the encapsulated compound is cryogenically ground to form the particulate compound where the shell acts as an anti -agglomerating agent, where the core is one of the alpha-olefins, such as 1 -hexene, 1 -octene, 1 -decene, 1- dodecene, 1 -tetradecene, and the like; isobutylene; alkyl acrylates; alkyl methacrylates.

[0008] The shell may be selected from the group comprising polybutylene, polymethacrylates, waxes, polyethylene glycol (PEG), polypropylene glycol (PPG), alkoxyl terminated PEG, polyethylene oxide (PEO), polypropylene oxide (PPO), stearic acid, polyethylene waxes, and mixtures thereof.

[0009] However, this solution discloses an encapsulated additive that is more difficult to produce, less easy to use, and which contains a small percentage of the active base relative to the total weight of the additive.

[0010] There is a prototype powder reagent reducing the hydrodynamic resistance of a turbulent flow of liquid hydrocarbons in pipelines (RU2743532C1, publ. on 2021.02.19), characterized by a high, not less than 75 wt% content of polyalphaolefin having the properties of reducing the hydrodynamic resistance of a turbulent flow of liquid hydrocarbons. However, the reagent additionally comprises a monofunctional heteroatomic organic compound with the number of carbon atoms from 3 to 16, containing oxygen, nitrogen as a heteroatom, and a bifunctional heteroatomic organic compound with the number of carbon atoms from 2 to 16, containing oxygen, nitrogen, sulfur, phosphorus as a heteroatom and a separating agent (antiagglomerating agent) with the following ratio of components in the composition, wt%: - finely dispersed polyalphaolefin powder - from 75 to 90,

- separating agent (antiagglomerator ) - from 2 to 15,

- monofunctional heteroatomic organic compound with the number of carbon atoms from 3 to 16 - from 1 to 10,

- bifunctional heteroatomic organic compound with the number of carbon atoms from 2 to 16 - from 1 to 10.

[0011] However, this solution discloses a polyalphaolefin reagent that cannot be used in case of transportation of heavy oil.

Summary

[0012] In one aspect of the solution, a reagent for reducing a hydrodynamic drag of a turbulent flow of hydrocarbon liquids in pipelines, comprising the following components, wt%:

A polyacrylate powder or crumb from 65 to 90;

A separating agent (anti-agglomerating agent) from 2 to 15;

A monofunctional heteroatomic organic compound with a carbon skeleton having a length from 3 to 16 units from 1 to 10;

A bifunctional heteroatomic organic compound with a carbon skeleton having a length from 2 to 16 units from 1 to 10;

A surfactant from 5 to 15.

[0013] In additional aspects, it is disclosed that the reagent comprises the polyacrylate powder with a mixture of glycol containing from 2 to 12 carbon atoms and fatty alcohol containing from 4 to 16 carbon atoms at a ratio of the polymer powder/the mixture of glycol and fatty alcohol making 85 weight parts/15 weight parts; the monofunctional heteroatomic organic compound is at least one of isomers of propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, isomers of tripropylamine, tributylamine, tripentylamine, trihexyl amine, triheptylamine, trioctylamine, trinonylamine, tridecylamine. triundecylamine, tridodecylamine, tritridecylamine, tritetradecylamine, tripentadecylamine, trihexadecylamine; the bifunctional heteroatomic organic compound is at least one of tripropyl phosphate, tributyl phosphate, tripentyl phosphate, propylene glycol, butylene glycol, butyl cellosolve, hexylene glycol, ethyl cellosolve, texanol, diethylene glycol, triethylene glycol, isophorone, morpholine, dioxane, dimethyl sulphoxide, dimethylformamide; the monofunctional heteroatomic organic compound of units is fatty alcohol containing from 4 to 16 carbon atoms; the bifunctional heteroatomic organic compound is a glycol containing from 2 to 12 carbon atoms; polyacrylates make from 75 to 90 wt%; polyacrylates make from 80 to 90 wt%; polyacrylates make from 85 to 90 wt%.

[0014] In another aspect of the solution, a method of transportation of a petroleum product through a pipeline is disclosed, comprising the following stages:

- injection of the specified reagent into the pipeline;

- transportation of the petroleum product containing the dissolved reagent.

[0015] The object of the invention is to prepare a reagent (drag reducing agent) for heavy oil containing a great amount of the active base to reduce the drag of the flow of liquid hydrocarbons, which can be injected as a powder.

[0016] The technical result of the solution involves the preparation of a solid stable drag reducing agent suitable for use in heavy oil and injection into the oil pipeline through any powder injection apparatus.

[0017] Essentially, a powder of polyacrylates is prepared by spray drying of latex containing polyacrylates used to reduce hydrodynamic drag, this powder is mixed with an antiagglomerating agent, a monofunctional heteroatomic organic compound with a carbon skeleton having a length from 3 to 16 units, a bifunctional heteroatomic organic compound a carbon skeleton having the length from 2 to 16 units, thus preparing a solid DRA. In this case, the mass fraction of polyacrylates is preferably from 65 to 90%, and more preferably from 75 to 90%.

[0018] The product prepared according to the described method is preferably fed into the flow of a hydrocarbon liquid transported through the pipeline using an injection apparatus that mechanically transfers the product through a screw auger or a screw feeder, for example, a screw extruder for polymeric materials, either directly into the flow of a hydrocarbon liquid or into an intermediate container for mixing the material with the liquid of the flow and by flowing the prepared mixture into the main flow of the pipeline.

Detailed description of the preferred embodiments

[0019] This section describes the main embodiment of the invention, which, however, does not limit other possible embodiments explicitly described in the application materials and apparent for a person skilled in the art.

[0020] The proposed reagent for reducing the hydrodynamic drag of the flow of liquid hydrocarbons in pipelines is prepared according to the following main procedure.

[0021] First, latex comprising polyacrylates to reduce the drag is prepared. The latex particles of a drag reducing agent can be formed by polymerizing at least one monomer selected from the group comprising acrylates, methacrylates, including, but not limited to, 2-Ethylhexyl methacrylate, isobutyl methacrylate, butyl methacrylate, acrylic acid, and combinations thereof. Namely, the latex polymers of the drag reducing agent are typically formed by polymerizing 2-Ethylhexyl methacrylate, isobutyl methacrylate, butyl methacrylate, acrylates, including, but not limited to, 2-Ethylhexyl acrylate, isobutyl acrylate, butyl acrylate, typically alcohol esters from Cl to CIO of acrylic acid or methacrylic acid, the small amounts of acrylic acid are also added to prepare a terpolymer. The latex particles of the drag reducing agent have a high molecular weight, set herein as exceeding a million g/mol.

[0022] The prepared liquid latex is dried by spray drying. The dried material is an active base powder with a particle size of 25-600 microns. This active base powder is mixed with polymer non-dissolving solvents to prepare a product with a polymer content of at least 65 wt. %, which is fed into the flow of a hydrocarbon liquid pumped through a pipeline using a polymer powder injection apparatus. The percentage of the active base in the additive is measured, first of all, according to the required amount of additional components, which ensure the possibility of using the additive, first of all, the possibility of injection of it in the form of a powder.

[0023] In another embodiment, the polymer is prepared in the form of crumbs. The crumb from can be prepared in one of the following ways:

- latex prepared by emulsion polymerization can be dried by any technically feasible method of drying materials, for example, by preparing sheets of dried polymer in infrared belt dryers, after which the dry polymer sheets are crushed in crushers for polymer materials to crumbs with size from 0.6 mm up to 1.5 cm,

- the powder prepared in the spray dryer with a particle size from 25 microns to 600 microns can be agglomerated in industrial agglomeration apparatus to crumbs ranging in size from 0.6 mm to 1.5 cm.

- direct drying of latex in rotary dryers to obtain crumbs ranging in size from 0.6 mm to 1.5 cm.

[0024] In case of use of the crumbs, the embodiments are possible, in which the agent is prepared by mixing the crumbs with an anti -agglomerating agent (up to 15% by weight) and this commodity form is transported to the station for feeding the agent into the oil pipeline. However, in this case, the station for injection of the agent must be adapted to injecting crumbs, and not powder, that is, it must be equipped with means for grinding the crumbs before feeding into the oil pipeline.

[0025] Calcium stearate, zinc stearate, ethylene bisstearamide, alcohol esters C6-C35 and stearic acid, talc, powder polymethyl methacrylate are used as anti -agglomerating agents. [0026] Mixtures of a monofunctional heteroatomic organic compound (MHOC) and a bifunctional heteroatomic organic compound (BHOC) are used as a polymer non-dissolving solvent, while organic compounds containing oxygen, nitrogen as a heteroatom - isomers of propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, isomers of tripropylamine, tributyl amine, tripentyl amine, trihexyl amine, triheptyl amine, tri octyl amine, trinonyl amine, tridecylamine, triundecylamine, tri dodecyl amine, tritridecylamine, tri tetradecyl amine, tripentadecylamine, trihexadecylamine can be used as MHOC; organic compounds containing oxygen, nitrogen, sulphur, phosphorus as a heteroatom - tripropyl phosphate, tributyl phosphate, tripentyl phosphate, propylene glycol, butylene glycol, butyl cellosolv, hexylene glycol, ethyl cellosolv, texanol, diethylene glycol, triethylene glycol, isophorone, morpholine, dioxane, dimethylsulfoxide, dimethylformamide, can be used as BHOC.

[0027] For mechanical mixing of polymer powder or crumbs with polymer non-dissolving solvents, mixers for powder polymer materials of any design can be used, for example, GebruderLodigeMaschinenbauGmbH (Germany), OOO Sibprommash (the Russian Federation, Novosibirsk).

[0028] For dosing a product containing great, not less than 65 wt% of polymer, injection apparatus can be used that mechanically move the product through a screw auger or screw feeder or similar companies KinematicaAG (Switzerland), IKA-WERKE GmbH & Co. KG (Germany), KraussMaffeiBerstorff AG (Germany) extruders or analogs.

[0029] Methods for preparation of a reagent for reducing the hydrodynamic drag of a flow of liquid hydrocarbons in pipelines are illustrated by the embodiments given below, but not limited to them.

Embodiment 1

[0030] Install a 250 ml jacketed three-necked flask at a Heidolph magnetic stirrer, connect a circulation thermostat to the flask jacket through silicone hoses.

[0031] Place a fluoroplastic-coated magnetic stirrer into the flask. Add 69.3 g of distilled water in a measuring glass into the flask, switch on the magnetic drive of the stirrer, the stirrer rotation speed is 800 rpm. While stirring, place a rubber septum into the neck of the flask, insert a 250 mm veterinary needle through the septum, with a nitrogen bottle from a reducer connected through a silicone hose, with a pressure of 0.01 MPa.

[0032] Add 55 g of 2-Ethylhexyl methacrylate to the reaction flask in the process of constant stirring and nitrogen supply. Then, add 5 g of sodium lauryl sulfate and 6.4 g of neonol 9-12 (other surfactants such as synthanol, sulfanol can be used) into the flask. Next, stir for about 15 minutes until sodium lauryl sulfate dissolves. Then, add 0.23 g of monosubstituted potassium phosphate and 0.18 g of disubstituted potassium phosphate to the reaction mass. Then, perform stirring and nitrogen purging for half an hour to remove the residual oxygen in the reaction mass.

[0033] After the nitrogen purging, add 0.2 g of ammonium persulphate (a source of radicals) to the reaction mass.

[0034] After adding the source of radicals, switch on a circulation thermostat for the circulation of the heat-transfer medium in the jacket of the reaction flask. Place a thermocouple in the reaction mass to measure the reaction temperature. Maintain the reaction temperature at 15 ± 1 ° C.

[0035] After the reaction mass reaches the set temperature, add a prepared solution of 0.1 g of Mohr's salt (initiating agent) in 40 g of distilled water with 0.01 mol/1 of sulfuric acid into the flask. The rate of adding the initiating agent solution is about 8 g/h.

[0036] Do not stop the stirring and nitrogen purging during the reaction time.

[0037] After the reaction, dry the prepared latex solution in the laboratory spray dryer at a temperature of 110 ± 5 °C. Subject to adding 2 g of anti-agglomerating agent that is calcium stearate.

[0038] Then, add 3.4 g of octanol and 3.4 g of hexylene glycol to the prepared powder and stir until smooth.

[0039] Assess the efficiency of the prepared reagent at a laboratory turborheometer. The drag reduction (DR) of the petroleum solvent in the capillary by the reagent was calculated according to the formula: is a coefficient of liquid drag; t is a time of flow of 330 cm ³ of petroleum solvent through the capillary o and p are indices related to the pure solvent and reagent solution, respectively.

[0040] The results of testing the efficiency of the agent prepared according to this embodiment are given in the Table 1 :

Table 1. Embodiment 2

[0041] Install a 250 ml jacketed three-necked flask at a Heidolph magnetic stirrer, connect a circulation thermostat to the flask jacket through silicone hoses.

[0042] Place a fluoroplastic-coated magnetic stirrer into the flask. Add 69.3 g of distilled water in a measuring glass into the flask, switch on the magnetic drive of the stirrer, the stirrer rotation speed is 800 rpm. While stirring, place a rubber septum into the neck of the flask, insert a 250 mm veterinary needle through the septum, with a nitrogen bottle from a reducer connected through a silicone hose, with a pressure of 0.01 MPa.

[0043] Add 55 g of isobutyl methacrylate to the reaction flask in the process of constant stirring and nitrogen supply. Then, add 3 g of sodium lauryl sulfate into the flask. Next, stir for about 15 minutes until sodium lauryl sulfate dissolves. Then, add 0.23 g of monosubstituted potassium phosphate and 0.18 g of disubstituted potassium phosphate to the reaction mass. Then, perform stirring and nitrogen purging for half an hour to remove the residual oxygen in the reaction mass.

[0044] After the nitrogen purging, add 0.2 g of ammonium persulphate (a source of radicals) to the reaction mass.

[0045] After adding the source of radicals, switch on a circulation thermostat for the circulation of the heat-transfer medium in the jacket of the reaction flask. Place a thermocouple in the reaction mass to measure the reaction temperature. Maintain the reaction temperature at 15 ± 1 ° C.

[0046] After the reaction mass reaches the set temperature, add a prepared solution of 0.1 g of Mohr's salt (initiating agent) in 40 g of distilled water with 0.01 mol/1 of sulfuric acid into the flask. The rate of adding the initiating agent solution is about 8 g/h.

[0047] Do not stop the stirring and nitrogen purging during the reaction time.

[0048] After the reaction, dry the prepared latex solution in the laboratory spray dryer at a temperature of 110 ± 5 °C. Subject to adding 1.17 g of anti-agglomerating agent that is zinc stearate to the dry product.

[0049] Then, add 0.59 g of propanol and 0.59 g of dimethyl sulfoxide to the prepared powder and stir until smooth.

[0050] The results of testing the efficiency of the agent prepared according to this embodiment are given in the Table 2:

Table 2.

Embodiment 3

[0051] Install a 250 ml jacketed three-necked flask at a Heidolph magnetic stirrer, connect a circulation thermostat to the flask jacket through silicone hoses.

[0052] Place a fluoroplastic-coated magnetic stirrer into the flask. Add 69.3 g of distilled water in a measuring glass into the flask, switch on the magnetic drive of the stirrer, the stirrer rotation speed is 800 rpm. While stirring, place a rubber septum into the neck of the flask, insert a 250 mm veterinary needle through the septum, with a nitrogen bottle from a reducer connected through a silicone hose, with a pressure of 0.01 MPa.

[0053] Add 55 g of butyl methacrylate to the reaction flask in the process of constant stirring and nitrogen supply. Then, add 5 g of sodium lauryl sulfate and 2.7 g of neonol 9-12 into the flask. Next, stir for about 15 minutes until sodium lauryl sulfate dissolves. Then, add 0.23 g of monosubstituted potassium phosphate and 0.18 g of disubstituted potassium phosphate to the reaction mass. Then, perform stirring and nitrogen purging for half an hour to remove the residual oxygen in the reaction mass.

[0054] After the nitrogen purging, add 0.2 g of ammonium persulphate (a source of radicals) to the reaction mass.

[0055] After adding the source of radicals, switch on a circulation thermostat for the circulation of the heat-transfer medium in the jacket of the reaction flask. Place a thermocouple in the reaction mass to measure the reaction temperature. Maintain the reaction temperature at 15 ± 1 ° C.

[0056] After the reaction mass reaches the set temperature, add a prepared solution of 0.1 g of Mohr's salt (initiating agent) in 40 g of distilled water with 0.01 mol/1 of sulfuric acid into the flask. The rate of adding the initiating agent solution is about 8 g/h.

[0057] Do not stop the stirring and nitrogen purging during the reaction time.

[0058] After the reaction, dry the prepared latex solution in the laboratory spray dryer at a temperature of 110 ± 5 °C. Subject to adding 5.7 g of anti-agglomerating agent that is zinc stearate to the dry product.

[0059] Then, add 8.8 g of tridecyl amine and 8.8 g of tripentyl phosphate to the prepared powder and stir until smooth. [0060] The results of testing the efficiency of the agent prepared according to this embodiment are given in the Table 3 :

Table 3.

Embodiment 4

[0061] Install a 250 ml jacketed three-necked flask at a Heidolph magnetic stirrer, connect a circulation thermostat to the flask jacket through silicone hoses.

[0062] Place a fluoroplastic-coated magnetic stirrer into the flask. Add 69.3 g of distilled water in a measuring glass into the flask, switch on the magnetic drive of the stirrer, the stirrer rotation speed is 800 rpm. While stirring, place a rubber septum into the neck of the flask, insert a 250 mm veterinary needle through the septum, with a nitrogen bottle from a reducer connected through a silicone hose, with a pressure of 0.01 MPa.

[0063] Add 55 g of 2-Ethylhexyl methacrylate and isobutyl methacrylate in equal proportion to the reaction flask in the process of constant stirring and nitrogen supply. Then, add 5.4 g of neonol 9-12 into the flask. Next, stir for about 15 minutes until sodium lauryl sulfate dissolves. Then, add 0.23 g of monosubstituted potassium phosphate and 0.18 g of disubstituted potassium phosphate to the reaction mass. Then, perform stirring and nitrogen purging for half an hour to remove the residual oxygen in the reaction mass.

[0064] After the nitrogen purging, add 0.2 g of ammonium persulphate (a source of radicals) to the reaction mass.

[0065] After adding the source of radicals, switch on a circulation thermostat for the circulation of the heat-transfer medium in the jacket of the reaction flask. Place a thermocouple in the reaction mass to measure the reaction temperature. Maintain the reaction temperature at 15 ± 1 ° C.

[0066] After the reaction mass reaches the set temperature, add a prepared solution of 0.1 g of Mohr's salt (initiating agent) in 40 g of distilled water with 0.01 mol/1 of sulfuric acid into the flask. The rate of adding the initiating agent solution is about 8 g/h.

[0067] Do not stop the stirring and nitrogen purging during the reaction time.

[0068] After the reaction, dry the prepared latex solution in the laboratory spray dryer at a temperature of 110 ± 5 °C. Subject to adding 12.8 g of anti-agglomerating agent that is talcum to the dry product. [0069] Then, add 6.1 g of decanol and 3 g of texanol to the prepared powder and stir until smooth.

[0070] The results of testing the efficiency of the agent prepared according to this embodiment are given in the Table 4:

Table 4.

[0071] As follows from the above tables, it may be concluded that the claimed reagent provides reduction of a hydrodynamic drag of a turbulent flow of heavy oils in pipelines and, as a result, provides ramp-up, and reduction in expenses for transporting a hydrocarbon liquid.

[0072] The embodiments are not limited to the embodiments described herein, other embodiments of the invention staying within the essence and scope of the present invention will be apparent for a person skilled in the sphere of technologies based on the information set forth and the knowledge of the state of art.

[0073] The elements in the singular do not exclude the plurality of the elements unless otherwise specified.

[0074] The methods disclosed herein comprise one or more steps or stages to implement the described solution. The steps and/or stages of the method can be substituted for each other staying within the claims of the invention. In other words, if a specific order of steps or stages is not established, the order and/or use of specific steps and/or stages may vary staying within the claims of the invention.

[0075] Although exemplary embodiments have been described in detail and shown in the accompanying drawings, it should be understood that such embodiments are illustrative only and are not used to limit the broader invention and that the invention should not be limited to the specific configurations and structures shown and described, as other various modifications may be apparent to the persons skilled in the relevant field.

[0076] The features mentioned in various dependent claims, as well as the implementations disclosed in various parts of the description, can be combined to achieve the advantageous effect, even if the possibility of such a combination is not disclosed explicitly.