CN113004460A - Low-temperature-resistant online viscosity-changing agent and preparation method thereof - Google Patents

Low-temperature-resistant online viscosity-changing agent and preparation method thereof Download PDF

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CN113004460A
CN113004460A CN202110355606.7A CN202110355606A CN113004460A CN 113004460 A CN113004460 A CN 113004460A CN 202110355606 A CN202110355606 A CN 202110355606A CN 113004460 A CN113004460 A CN 113004460A
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agent
parts
temperature
long
polyoxyethylene ether
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CN113004460B (en
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荣敏杰
孙建波
许永升
于庆华
荣帅帅
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Shandong Nuoer Biological Technology Co Ltd
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Shandong Nuoer Biological Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/64—Oil-based compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Abstract

The invention relates to a low-temperature-resistant online viscosity-changing agent and a preparation method thereof. Fully and uniformly mixing an aqueous phase solution, an oil phase solution, an azo initiator and an oxidant, emulsifying, pumping a reducing agent to initiate polymerization, adding a long-chain flexible monomer in the polymerization process, adding a hydrolyzing agent after the reaction is finished, hydrolyzing, adding a phase inversion agent, and uniformly stirring to obtain the viscosity reducer; the aqueous phase solution comprises acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, sodium hydroxide, a structure regulator, a pour point depressant and water; the oil phase solution comprises an oily solvent, an emulsifier, a suspending agent and a penetrating agent. The viscosity modifier prepared by the invention has the characteristic of dual purposes by one dose, has extremely high resistance reduction effect under the condition of low-concentration polymer solution, and has excellent thickening and sand carrying effects after the concentration of the polymer is properly increased.

Description

Low-temperature-resistant online viscosity-changing agent and preparation method thereof
Technical Field
The invention relates to the technical field of oilfield fracturing yield increase, in particular to a composition for preparing a low-temperature-resistant online viscosity-changing agent, a low-temperature-resistant online viscosity-changing agent prepared from the composition and a preparation method of the low-temperature-resistant online viscosity-changing agent.
Background
In recent years, the rising speed of the proportion of low-permeability reserves in the oil and gas exploration reserves is increased year by year. The permeability and the porosity of the low-permeability oil and gas reservoir are low, the heterogeneity is strong, the productivity is found after most of oil and gas wells need fracturing production-increasing measures, and the fracturing production-increasing technology has increasingly obvious effect in the development of the low-permeability oil and gas reservoir.
Due to the progress of the fracturing fluid technology and the requirements of oil field construction, the on-line fracturing fluid construction technology is rapidly developed, a fluid preparation station, a preparation pool or other preparation equipment is not needed in the technology, high-content concentrated emulsion is directly pumped to a sand mixing truck according to the proportion through a gear pump in an on-site on-line adding mode, a propping agent and water are added, and the water, the propping agent and chemicals are mixed together according to the proportion under the stirring of the sand mixing truck. However, because the effects of the drag reducer and the thickening agent are different, the agents need to be frequently switched in the oil field construction process, and certain inconvenience is brought to field construction. Therefore, higher requirements are put on the fracturing fluid medicament, and the fracturing fluid medicament is required to have not only excellent resistance reduction performance but also high-viscosity sand suspending performance. Therefore, the online fracturing fluid viscosity modifier has important significance for oil field development.
The Chinese patent application CN201811646387.2 discloses a preparation method of a temperature-resistant and salt-resistant fracturing fluid thickening agent, and the temperature-resistant and salt-resistant fracturing fluid thickening agent prepared by the method can achieve a good sand suspending effect without being crosslinked with a crosslinking agent, and has good temperature resistance and salt resistance. However, the CN201811646387.2 patent application discloses a temperature-resistant and salt-resistant fracturing fluid thickener which cannot be used as a drag reducer, and the product is a dry powder particle type product, and the dissolution and aging time is more than 1 hour in the using process.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a low-temperature-resistant online adhesion promoter and a preparation method thereof. The low-temperature-resistant online viscosity-changing agent prepared by the invention has the characteristic of dual purposes by one agent, has extremely high resistance-reducing effect under the condition of low-concentration polymer solution, and has excellent thickening and sand-carrying effects after the concentration of the polymer is properly increased. The low-temperature-resistant online variable binder prepared by the invention can realize online continuous operation, is convenient to operate, does not need a liquid preparation station, a preparation pool or other preparation equipment, can save the operation time and improve the fracturing yield-increasing efficiency of an oil field.
The present invention provides in a first aspect a composition for preparing a low temperature on-line tack-reducing agent, the composition comprising a dispersed aqueous phase, a continuous oil phase and a process treatment; the dispersed water phase comprises the following components in parts by weight: 100-150 parts of acrylamide, 150-200 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40-60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5-10 parts of long-chain flexible monomer, 29-38 parts of sodium hydroxide, 0.05-0.2 part of structure regulator, 50-80 parts of pour point depressant and 200-330 parts of water; the continuous oil phase comprises the following components in parts by weight: 180-260 parts of an oily solvent, 20-40 parts of an emulsifier, 1-5 parts of a suspending agent and 5-10 parts of a penetrating agent; the process treating agent comprises the following components in parts by weight: 0.02-0.5 part of initiator, 16-33 parts of hydrolytic agent and 25-35 parts of phase inversion agent.
Preferably, the long-chain flexible monomer is one or more of N-octadecyl acrylamide, octadecyl acrylate and methacrylamide octadecanol polyoxyethylene ether; the structure regulator is N, N-methylene bisacrylamide and/or pentaerythritol triallyl ether; and/or the pour point depressant is one or more of sodium chloride, sodium acetate and glycol.
Preferably, the oily solvent is one or more of kerosene, diesel oil, aviation kerosene, mineral oil and white oil, and preferably, the oily solvent is low-temperature resistant white oil with the freezing point lower than-30 ℃; the emulsifier is one or more of span 80, cetearyl alcohol polyoxyethylene ether-10, isomeric tridecanol polyoxyethylene ether 1303, isomeric tridecanol polyoxyethylene ether 1305, isomeric tridecanol polyoxyethylene ether 1307, isomeric tridecanol polyoxyethylene ether 1309, propylene glycol block polyether L61, propylene glycol block polyether L31, propylene glycol block polyether L42, propylene glycol block polyether L63, Tween 60, castor oil polyoxyethylene ether EL-10, castor oil polyoxyethylene ether EL-20 and castor oil polyoxyethylene ether EL-30; and/or the water-oil balance value of the emulsifier is 6-8.
Preferably, the suspending agent is one or more of hydrophobic silica, modified bentonite and modified hectorite; and/or the penetrating agent is one or more of dioctyl sodium sulfosuccinate, fatty alcohol-polyoxyethylene ether JFC-U and isooctanol-polyoxyethylene ether JFC-E.
Preferably, the initiator is a composite initiation system, and the composite initiation system comprises an azo initiator, an oxidizing agent and a reducing agent; the azo initiator is one or more of azobisisobutyramidine dihydrochloride, azobisisoheptonitrile and azobisisobutyrimidazoline hydrochloride, the oxidizing agent is potassium persulfate, and the reducing agent is sodium bisulfite; the hydrolytic agent is one or more of sodium hydroxide, potassium hydroxide and sodium bicarbonate; and/or the phase inversion agent is fatty alcohol-polyoxyethylene ether and/or nonylphenol polyoxyethylene ether.
The invention provides a preparation method of a low-temperature-resistant online adhesion promoter, which is prepared by adopting the composition for preparing the low-temperature-resistant online adhesion promoter, and comprises the following steps:
(a) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, a structure regulator and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 6.5-7.5 to obtain a second mixed solution, adding a pour point depressant into the second mixed solution, and fully dissolving the pour point depressant in the second mixed solution to obtain an aqueous phase solution;
(b) uniformly mixing an oily solvent, an emulsifier, a suspending agent and a penetrating agent to obtain an oil phase solution;
(c) adding the water phase solution, the azo initiator and the oxidant into the oil phase solution and uniformly mixing to obtain an emulsion solution;
(d) adjusting the temperature of the emulsion solution to 10-25 ℃, introducing nitrogen to remove oxygen, adding a reducing agent to initiate polymerization, and adding a long-chain flexible monomer to perform polymerization in the polymerization process to obtain a polymerization emulsion;
(e) adding a hydrolytic agent into the polymerized emulsion for heat preservation treatment to obtain heat preservation treatment liquid;
(f) and cooling the heat preservation treatment liquid to 20-30 ℃, adding a phase inversion agent into the heat preservation treatment liquid, and uniformly stirring to obtain the low-temperature-resistant online adhesion promoter.
Preferably, during the polymerization reaction, the long-chain flexible monomer is divided into three parts and added sequentially, wherein the adding mode is as follows: adding a first part of long-chain flexible monomers for polymerization reaction after initiating polymerization reaction, adding a second part of long-chain flexible monomers for polymerization reaction after reacting for 1h, and adding a third part of long-chain flexible monomers for polymerization reaction after reacting for 1.5h to obtain polymerization emulsion.
Preferably, the first part of long-chain flexible monomers and the second part of long-chain flexible monomers are both 30 wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40 wt.% of the total amount of the long-chain flexible monomers; and/or continuing the polymerization reaction for 1.5-2.5 hours at the temperature of 60-65 ℃ after the third part of the long-chain flexible monomer is added.
Preferably, in the step (b), the oily solvent, the emulsifier, the co-emulsifier and the penetrant are uniformly mixed at a stirring speed of 800-2000 rpm; in the step (c), adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes at a stirring speed of 1000-2000 rpm to obtain the emulsion solution; in the step (d), adding a reducing agent into the emulsion solution at a stirring speed of 200-500 rpm to initiate polymerization; in the step (e), the temperature of the heat preservation treatment is 60-65 ℃, and the time of the heat preservation treatment is 3-6 hours; and/or in the step (f), adding the phase inversion agent into the polymerization emulsion at a stirring speed of 500-1000 rpm, and stirring for 2-3 hours to obtain the low-temperature-resistant online adhesion promoter.
In a third aspect, the present invention provides a low temperature in-line tack-reducing agent produced by the production method according to the second aspect of the present invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the viscosity modifier provided by the invention adopts an inverse emulsion polymerization process, and the molecular weight of the polymer is larger and the viscosity is higher through a mode of copolymerization before hydrolysis. The composition for preparing the low-temperature-resistant online viscosity-changing agent comprises the following components which contribute to preparing the viscosity-changing agent polymer emulsion: a large amount of AMPS (namely 2-acrylamide-2-methylpropanesulfonic acid) and methacryloyloxyethyl-N, N-dimethyl propane sulfonate are added into the viscosity modifier, so that the temperature resistance and salt resistance of the polymer are improved; the structure regulator and the long-chain flexible monomer are added, and micro-crosslinking and association space network structures are generated among polymer molecular chains, so that the temperature resistance and salt resistance of the polymer are improved, the sand carrying performance of the polymer is improved, the internal rotation freedom degree of the polymer molecular chains is relatively improved by the long-chain flexible monomer, and the capacity of reducing the flow resistance of the polymer emulsion in a turbulent flow state is improved; the pour point depressant and the low-temperature resistant white oil are added, so that the freezing point of the polymer emulsion is lower than-20 ℃, the viscosity modifier disclosed by the invention can be suitable for being used for low-temperature environment operation, and the problems that the emulsion polymer becomes solid and can not flow and the construction difficulty is increased after the temperature of the emulsion polymer is too low in Changqing oil fields and Daqing oil fields in winter can be solved; the suspending agent is added, so that a polymer emulsion system is more stable, polymer colloidal particles are more uniformly dispersed in the emulsion, the phenomenon of adhesion and demulsification among the colloidal particles is not easy to occur, and the quality guarantee period of the emulsion is prolonged; the addition of the penetrant greatly increases the dissolution rate of the polymer emulsion, especially in saline.
(2) Different from the drag reducer or the thickening agent which only has single function and is used in the oil field construction process in the prior art, the invention synthesizes the low-temperature-resistant on-line viscosity changer with the characteristic of one agent for two purposes, and the viscosity changer can be used as a fracturing fluid slick water drag reducer and a fracturing fluid thickening agent; in the using process, a liquid preparation station, a preparation pool or other preparation equipment is not needed, the high-content concentrated liquid active chemical is directly pumped to the sand mixing truck in proportion through a gear pump in an on-site online adding mode, the proppant and the water are added, and the water, the proppant and the chemical are mixed together according to the proportion under the stirring of the sand mixing truck. The viscosity modifier has extremely high drag reduction effect under the condition of low-concentration polymer solution, and has excellent thickening and sand-carrying effects after the polymer concentration is properly increased. Compared with a dry powder particle type temperature-resistant salt-resistant fracturing fluid thickening agent product which cannot be used as a drag reducer in CN201811646387.2, the low-temperature-resistant online viscosity changer prepared by the invention is a water-in-oil emulsion product, can be used as a drag reducer and a thickening agent, has high dissolution speed and can realize online continuous operation.
(3) The low-temperature-resistant online variable viscosity agent provided by the invention has the advantages of low temperature resistance, good stability, long shelf life, fast product dissolution, small addition amount, high drag reduction rate, strong salt resistance, good sand suspending effect, low viscosity after gel breaking, complete flowback, less residue and the like, and is an environment-friendly online fracturing fluid variable viscosity agent.
Drawings
FIG. 1 is a resistance-reducing performance test curve of the low-temperature-resistant online adhesion promoter in embodiments 1 to 3 of the present invention.
FIG. 2 is a rheological property test curve of the low temperature resistant online adhesion promoter in examples 1 to 3 of the present invention. In fig. 2, the left ordinate is the test temperature; t ═ f (T) represents the test temperature profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The present invention provides in a first aspect a composition for preparing a low temperature on-line tack-reducing agent, the composition comprising a dispersed aqueous phase, a continuous oil phase and a process treatment; the dispersed water phase comprises the following components in parts by weight: 100-150 parts (e.g., 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150 parts) of acrylamide, 150-200 parts (e.g., 150, 155, 160, 165, 170, 175, 180, 185, 190, 195 or 200 parts) of 2-acrylamido-2-methylpropanesulfonic acid, 40-60 parts (e.g., 40, 45, 50, 55 or 60 parts) of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5-10 parts (e.g., 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 parts) of long-chain flexible monomer, 29-38 parts (e.g., 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5 or 38 parts) of sodium hydroxide, 0.05-0.05 parts (e.0.05-0.08, 0.15, 0.08-0.50, 0.5, 0.05-0.0.15, 0.50 parts (e.0.08-0.1, or 200 parts) of a pour point depressant, 0.5 parts (e, 55. 60, 65, 70, 75, or 80 parts), 200-330 parts of water (e.g., 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, or 330 parts); the continuous oil phase comprises the following components in parts by weight: 180-260 parts (such as 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255 or 260 parts) of an oily solvent, 20-40 parts (such as 20, 25, 30, 35 or 40 parts) of an emulsifier, 1-5 parts (such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 parts) of a suspending agent, and 5-10 parts (such as 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 parts) of a penetrating agent; the process treating agent comprises the following components in parts by weight: 0.02-0.5 part (such as 0.02, 0.04, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5 part) of initiator, 16-33 parts (such as 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32 or 33 parts) of hydrolytic agent, and 25-35 parts (such as 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 parts) of phase transfer agent. In some embodiments of the present invention, the unit "parts by weight" of each component contained in the composition for preparing the low temperature-resistant in-line tackiness agent may be collectively referred to as "g" or "kg". The low-temperature-resistant online viscosity-changing agent prepared by the composition is of a water-in-oil structure, the oil phase is used as a continuous phase, the water phase is used as a dispersed phase, and the water phase exists in a system in a form of nanoparticles and is wrapped by the emulsifier and the oil phase.
The composition for preparing the low-temperature-resistant online viscosity-changing agent has a proper component ratio, and comprises the following components which contribute to preparing the viscosity-changing agent polymer emulsion: a large amount of AMPS and methacryloxyethyl-N, N-dimethyl propanesulfonate can improve the temperature resistance and salt resistance of the prepared variable-viscosity agent polymer; the structure regulator and the long-chain flexible monomer can enable the molecular chains of the viscosity-changing agent polymer to generate micro-crosslinking and associate with a spatial network structure, so that the temperature resistance and salt resistance of the polymer can be improved, the sand carrying performance of the polymer is improved, the internal rotation freedom degree of the polymer molecular chains is relatively improved by the flexible monomer, and the capacity of reducing the flow resistance of the polymer emulsion in a turbulent flow state is improved; the pour point depressant and the oily solvent are preferably low-temperature resistant white oil, for example, the freezing point of a polymer emulsion of the viscosity modifier can be lower than-20 ℃, so that the viscosity modifier can be suitable for low-temperature environment operation, and the problems that the temperature of a Changqing oil field and a Daqing oil field is lower in winter, and the emulsion polymer becomes solid and can not flow after being too low in temperature, and the construction difficulty is increased can be solved; the suspending agent can make a polymer emulsion system more stable, so that polymer colloidal particles are dispersed in the emulsion more uniformly, the phenomenon of adhesion and demulsification among the colloidal particles is not easy to occur, and the quality guarantee period of the variable-viscosity agent polymer emulsion can be prolonged; the penetrant can greatly improve the dissolution rate of the polymer emulsion of the viscosity-changing agent, especially in saline water.
According to some preferred embodiments, the long-chain flexible monomer is one or more of N-octadecyl acrylamide, octadecyl acrylate, methacrylamido-octadecyl alcohol polyoxyethylene ether; the structure regulator is N, N-methylene bisacrylamide and/or pentaerythritol triallyl ether; in the invention, the preferable long-chain flexible monomer and the structure regulator are added, so that micro-crosslinking and association of a spatial network structure are generated among polymer molecular chains, the temperature resistance and salt resistance of the polymer are improved, the sand carrying performance of the polymer is improved, the internal rotation freedom degree of the polymer molecular chains is relatively improved by the flexible monomer, and the capacity of reducing the flow resistance of the polymer emulsion in a turbulent flow state is improved; in the invention, the long-chain flexible monomer is a monomer with internal rotation freedom of chemical bonds on a main chain; the addition of the long-chain flexible monomer and the relatively rigid monomer can improve the flexibility of the polymer molecular chain and improve the ability of the polymer emulsion to reduce the flow resistance in a turbulent flow state; in the invention, the structure regulator is introduced monomer capable of generating micro-crosslinking structure, and can improve the temperature resistance and salt resistance of the polymer and improve the sand carrying performance of the polymer.
According to some preferred embodiments, the pour point depressant is one or more of sodium chloride, sodium acetate, ethylene glycol.
According to some preferred embodiments, the oily solvent is one or more of kerosene, diesel oil, jet fuel oil, mineral oil, white oil, preferably, the oily solvent is white oil; more preferably, the oily solvent is a low temperature resistant white oil having a freezing point of less than-30 ℃, and in the present invention, the low temperature resistant white oil having a freezing point of less than-30 ℃ is, for example, a D110 white oil produced in a petroleum refinery of zilu petrochemical industry; the emulsifier is one or more of span 80, cetearyl alcohol polyoxyethylene ether-10, isomeric tridecanol polyoxyethylene ether 1303, isomeric tridecanol polyoxyethylene ether 1305, isomeric tridecanol polyoxyethylene ether 1307, isomeric tridecanol polyoxyethylene ether 1309, propylene glycol block polyether L61, propylene glycol block polyether L31, propylene glycol block polyether L42, propylene glycol block polyether L63, Tween 60, castor oil polyoxyethylene ether EL-10, castor oil polyoxyethylene ether EL-20 and castor oil polyoxyethylene ether EL-30; preferably, the emulsifier is a compound emulsifier system of multiple (two or more) selected from span 80, cetearyl alcohol polyoxyethylene ether-10, isomeric tridecanol polyoxyethylene ether 1303, isomeric tridecanol polyoxyethylene ether 1305, isomeric tridecanol polyoxyethylene ether 1307, isomeric tridecanol polyoxyethylene ether 1309, propylene glycol block polyether L61, propylene glycol block polyether L31, propylene glycol block polyether L42, propylene glycol block polyether L63, tween 60, castor oil polyoxyethylene ether EL-10, castor oil polyoxyethylene ether EL-20 and castor oil polyoxyethylene ether EL-30; and/or the emulsifier has a water-oil balance value (HLB value) of 6-8.
According to some preferred embodiments, the suspending agent is one or more of hydrophobic silica, modified bentonite, modified hectorite; in the present invention, the modified hectorite, also called organic hectorite, refers to a hydrophobically modified hectorite, which is modified with a quaternary ammonium cationic surfactant; in the present invention, both the hydrophobic silica and the modified hectorite are hydrophobically modified, soluble in an oily solvent and insoluble in water; the present invention has no particular requirement on the type of the hydrophobic silica, and the hydrophobic silica may be, for example, WACKER HDK H20 hydrophobic silica manufactured by wacker chemical (china) ltd; and/or the penetrating agent is one or more of dioctyl sodium sulfosuccinate, fatty alcohol-polyoxyethylene ether JFC-U and isooctanol-polyoxyethylene ether JFC-E. In the present invention, the suspending agent is an oil-soluble suspending agent, which is a substance capable of keeping fine particles in a slurry in a suspended state; the dispersion degree is high, the surface area is large, and the adsorption force is strong; the invention improves the stability of the emulsion system by introducing the suspending agent. In the invention, the penetrant is a surfactant, which can improve the distribution state of the emulsifier around the dispersed phase and improve the dissolution speed of the polymer emulsion, thereby improving the drag reduction performance of the polymer emulsion.
According to some preferred embodiments, the initiator is a complex initiation system comprising an azo-based initiator, an oxidizing agent and a reducing agent; the azo initiator is one or more of azobisisobutyramidine dihydrochloride, azobisisoheptonitrile and azobisisobutyrimidazoline hydrochloride, the oxidizing agent is potassium persulfate, and the reducing agent is sodium bisulfite; the hydrolytic agent is one or more of sodium hydroxide, potassium hydroxide and sodium bicarbonate; and/or the phase inversion agent is fatty alcohol-polyoxyethylene ether and/or nonylphenol polyoxyethylene ether.
The invention provides a preparation method of a low-temperature-resistant online adhesion promoter, which is prepared by adopting the composition for preparing the low-temperature-resistant online adhesion promoter in the first aspect, namely the raw material for preparing the low-temperature-resistant online adhesion promoter, and comprises the following steps:
(a) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, a structure regulator and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 6.5-7.5 (such as 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4 or 7.5) preferably to 7.0 to obtain a second mixed solution, and adding a pour point depressant into the second mixed solution to fully dissolve the pour point depressant into the second mixed solution to obtain an aqueous phase solution; in the invention, preferably, the pH value of the first mixed solution is adjusted to 6.5-7.5, and then the pour point depressant is added, so as to avoid the problem that the pour point depressant is added in advance and may react with sodium hydroxide; in some embodiments, after adding the pour point depressant to the second mixed solution and fully dissolving the pour point depressant in the second mixed solution to obtain the aqueous phase solution, the method further comprises the step of testing (re-testing) the pH of the aqueous phase solution and keeping the pH value of the aqueous phase solution between 6.5 and 7.5, so that the problem that the pH value is slightly changed due to the addition of the pour point depressant can be avoided.
(b) Uniformly mixing an oily solvent, an emulsifier, a suspending agent and a penetrating agent to obtain an oil phase solution; in the present invention, the oily solvent, the emulsifier, the penetrant and the suspending agent are mixed, for example, preferably at a stirring speed of 1000 to 2000rpm, until the suspending agent is uniformly dispersed, to obtain the oil phase solution.
(c) Adding the water phase solution, the azo initiator and the oxidant into the oil phase solution and uniformly mixing to obtain an emulsion solution; in the present invention, it is preferable that the aqueous phase solution, the azo initiator and the oxidizing agent are added to the oil phase solution at a uniform rate within 10 to 20 minutes at a stirring speed of, for example, 1000 to 2000rpm to obtain the emulsion solution of a uniform emulsion.
(d) Adjusting the temperature of the emulsion solution to 10-25 ℃ (for example, 10 ℃, 15 ℃, 20 ℃ or 25 ℃), introducing nitrogen to remove oxygen, for example, introducing nitrogen to remove oxygen for 30min, then adding a reducing agent to initiate polymerization reaction, and adding a long-chain flexible monomer to carry out polymerization reaction in the polymerization reaction process to obtain a polymerization emulsion; in the invention, specifically, for example, the system temperature of the emulsion solution is adjusted to 25 ℃, nitrogen is introduced to remove oxygen for 30min, a reducing agent is pumped to initiate polymerization at a stirring speed of 200 to 500rpm, after initiation of polymerization, 30 wt.% of the long-chain flexible monomer is added to the system, for example, after reaction at 35 ℃ for 1h, 30 wt.% of the long-chain flexible monomer is added, for example, after reaction at 45 ℃ for 1.5h, the remaining 40 wt.% of the long-chain flexible monomer is added, the polymerization temperature is controlled at 60 ℃, and after reaction for 2h, the reaction is ended, so as to obtain the polymerization emulsion.
(e) Adding a hydrolytic agent into the polymerized emulsion for heat preservation treatment to obtain heat preservation treatment liquid; in the invention, specifically, for example, at a stirring speed of 500-1000 rpm, a hydrolyzing agent is added into the polymerization emulsion for heat preservation treatment for 4 hours to obtain a heat preservation treatment liquid; in the invention, the addition of the hydrolyzing agent can hydrolyze part of amide groups in the polyacrylamide emulsion into carboxylic acid groups, the hydrolyzed carboxylic acid groups are more uniformly distributed in a molecular chain, the hydrolysis degree of the polymer is increased, and the viscosity of the polymer emulsion can be effectively improved.
(f) Cooling the heat preservation treatment liquid to 20-30 ℃ (for example, 20 ℃, 25 ℃ or 30 ℃), adding a phase transfer agent into the heat preservation treatment liquid, and uniformly stirring to obtain a low-temperature-resistant online adhesion promoter (abbreviated as adhesion promoter); in the invention, specifically, for example, after the heat preservation is finished, the heat preservation treatment liquid is cooled to 30 ℃, a phase inversion agent is added at the stirring speed of 500-1000 rpm, and the mixture is continuously stirred for 2 hours to obtain a brown yellow liquid as a low-temperature online viscosity-changing resistant agent; in the invention, the low-temperature-resistant online viscosity modifier is also marked as a low-temperature-resistant online fracturing fluid viscosity modifier; the low-temperature-resistant online viscosity-changing agent prepared by the invention has a water-in-oil structure, an oil phase is used as a continuous phase, a water phase is used as a dispersed phase, and the water phase exists in a system in a form of nano particles and is wrapped by an emulsifier and the oil phase.
In the invention, the low-temperature on-line viscosity-changing agent is prepared from the following raw materials in parts by weight:
100-150 parts of acrylamide, 150-200 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40-60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5-10 parts of long-chain flexible monomer, 29-38 parts of sodium hydroxide, 0.05-0.2 part of structure regulator, 50-80 parts of pour point depressant, 200-330 parts of water, 180-260 parts of oily solvent, 20-40 parts of emulsifier, 1-5 parts of suspending agent, 5-10 parts of penetrating agent, 0.02-0.5 part of initiator, 16-33 parts of hydrolytic agent and 25-35 parts of phase transfer agent; in the invention, when the long-chain flexible monomer is preferably divided into three parts to be sequentially added, the using amount of the long-chain flexible monomer is 5-10 parts, which refers to the total using amount of the three parts of the long-chain flexible monomer.
The preparation method comprises the steps of preparing a water phase, an oil phase, emulsification, polymerization and post-treatment; the anti-low temperature on-line viscosity-changing agent is prepared from raw materials such as acrylamide, methacryloyloxyethyl-N, N-dimethyl propane sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, a long-chain flexible monomer, a structure regulator and the like by adopting an inverse emulsion polymerization process and a method of copolymerization and hydrolysis, and the prepared viscosity-changing agent polymer has larger molecular weight and higher viscosity. A large amount of AMPS and methacryloyloxyethyl-N, N-dimethyl propanesulfonate are added into the viscosity-changing agent, so that the temperature resistance and salt resistance of the polymer are improved; the structure regulator and the long-chain flexible monomer are added, and micro-crosslinking and association space network structures are generated among polymer molecular chains, so that the temperature resistance and salt resistance of the polymer are improved, the sand carrying performance of the polymer is improved, the internal rotation freedom degree of the polymer molecular chains is relatively improved by the flexible monomer, and the capacity of reducing the flow resistance of the polymer emulsion in a turbulent flow state is improved; the pour point depressant and the low-temperature resistant white oil are added, so that the freezing point of the polymer emulsion is lower than-20 ℃, the viscosity modifier disclosed by the invention can be suitable for being used for low-temperature environment operation, and the problems that the emulsion polymer becomes solid and can not flow and the construction difficulty is increased after the temperature of the emulsion polymer is too low in Changqing oil fields and Daqing oil fields in winter can be solved; the suspending agent is added, so that a polymer emulsion system is more stable, polymer colloidal particles are more uniformly dispersed in the emulsion, the phenomenon of adhesion and demulsification among the colloidal particles is not easy to occur, and the quality guarantee period of the emulsion is prolonged; the addition of the penetrant greatly increases the dissolution rate of the polymer emulsion, especially in saline.
The low-temperature-resistant online viscosity modifier prepared by the invention has the characteristic of dual purposes by one agent, has extremely high resistance-reducing effect under the condition of low-concentration polymer solution, and has excellent thickening and sand-carrying effects after the concentration of the polymer is properly increased; the viscosity modifier can be used as a slickwater drag reducer of the fracturing fluid and a thickening agent of the fracturing fluid. The low-temperature-resistant online variable binder prepared by the invention can realize online continuous operation, is convenient to operate, does not need a liquid preparation station, a preparation pool or other preparation equipment, can save the operation time and improve the fracturing yield-increasing efficiency of an oil field. The low-temperature-resistant online variable viscosity agent prepared by the invention has the advantages of low temperature resistance, good stability, long shelf life, quick product dissolution, small addition amount, high drag reduction rate, strong salt resistance, good sand suspending effect, low viscosity after gel breaking, complete flowback, less residue and the like, and is an environment-friendly online fracturing fluid variable viscosity agent.
According to some preferred embodiments, during the polymerization, the long-chain flexible monomer is added in three portions in sequence: after the initiation of the polymerization reaction, adding a first part of long-chain flexible monomers to perform a polymerization reaction, for example, reacting at 35 ℃ for 1 hour, then adding a second part of long-chain flexible monomers to continue the polymerization reaction, for example, reacting at 45 ℃ for 1.5 hours, then adding a third part of long-chain flexible monomers to continue the polymerization reaction, thereby obtaining a polymerization emulsion. In the invention, the addition of the long-chain flexible monomer and the relatively rigid monomer can improve the flexibility of the polymer molecular chain and improve the ability of the polymer emulsion to reduce the flow resistance in a turbulent flow state; after the monomer is added, a molecular chain has an association effect, the distribution rule of the long-chain flexible monomer in the molecular chain has a large influence on the viscosity of the polymer, and the monomer is added in a segmented manner to improve the distribution of the long-chain flexible monomer, reduce the intra-molecular association and increase the intermolecular association effect.
According to some preferred embodiments, the long-chain flexible monomers consist of a first portion of long-chain flexible monomers, a second portion of long-chain flexible monomers, and a third portion of long-chain flexible monomers; the first part of long-chain flexible monomers and the second part of long-chain flexible monomers are both 30 wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40 wt.% of the total amount of the long-chain flexible monomers; in the present invention, wt.% means mass percentage.
According to some preferred embodiments, the polymerization reaction is continued for 1.5 to 2.5 hours (e.g., 1.5, 2, or 2.5 hours) at a temperature of 60 to 65 ℃ after the third portion of the long-chain flexible monomer is added.
According to some preferred embodiments, in the step (b), the oily solvent, the emulsifier, the co-emulsifier and the penetrating agent are uniformly mixed at a stirring speed of 800-2000 rpm until the suspending agent is uniformly dispersed; in the step (c), adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes at a stirring speed of 1000-2000 rpm to obtain the emulsion solution; in the invention, the water phase solution, the azo initiator and the oxidant are sequentially added into the oil phase solution at a uniform speed within 10-20 minutes; preferably, the water phase solution, the azo initiator and the oxidant are added into the oil phase solution at a uniform speed within 10-20 minutes to obtain the emulsion solution, so that the emulsification is more stable; in the step (d), adding a reducing agent into the emulsion solution at a stirring speed of 200-500 rpm to initiate polymerization; in the step (e), the temperature of the heat preservation treatment is 60-65 ℃, and the time of the heat preservation treatment is 3-6 h (for example, 3, 3.5, 4, 4.5, 5, 5.5 or 6 h); and/or in the step (f), adding the phase inversion agent into the polymerization emulsion at a stirring speed of 500-1000 rpm, and stirring for 2-3 hours to obtain the low-temperature-resistant online adhesion promoter.
According to some embodiments, the method for preparing the low-temperature-resistant online adhesion promoter comprises the following steps:
(a) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, a structure regulator and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, adding a pour point depressant into the second mixed solution, fully dissolving, and then repeatedly measuring the pH value to make the pH value to 7.0 to obtain an aqueous phase solution;
(b) mixing an oily solvent, an emulsifier, a penetrating agent and a suspending agent at a stirring speed of 1000-2000 rpm until the suspending agent is uniformly dispersed to obtain an oil phase solution;
(c) adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes at a stirring speed of 1000-2000 rpm to obtain an emulsion solution of a uniform emulsion;
(d) adjusting the system temperature of the emulsion solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping a reducing agent at a stirring speed of 200-500 rpm to initiate polymerization, adding 30 wt.% of long-chain flexible monomer into the system after the initiation of polymerization, adding 30 wt.% of long-chain flexible monomer after reacting for 1h, adding the remaining 40 wt.% of long-chain flexible monomer after reacting for 1.5h, controlling the temperature at 60 ℃, and ending the reaction after continuously reacting for 2h to obtain a polymerization emulsion;
(e) after the reaction is finished, adding a hydrolytic agent into the polymerized emulsion at a stirring speed of 500-1000 rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
(f) and after the heat preservation is finished, cooling the heat preservation treatment liquid to 30 ℃, adding a phase inversion agent at the stirring speed of 500-1000 rpm, and continuously stirring for 2 hours to obtain a brown yellow liquid as the low-temperature-resistant online adhesion promoter.
In a third aspect, the present invention provides a low temperature in-line tack-reducing agent produced by the production method according to the second aspect of the present invention.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
The composition for preparing the low temperature resistant on-line viscosity modifier in this example consists of a dispersed water phase, a continuous oil phase and a process treatment agent;
the dispersed water phase comprises the following components in parts by weight:
100 parts of acrylamide, 150 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5 parts of N-octadecyl acrylamide (long-chain flexible monomer), 29 parts of sodium hydroxide, 0.05 part of N, N-methylene bisacrylamide (structure regulator), 50 parts of sodium chloride (pour point depressant) and 300 parts of water;
the continuous oil phase comprises the following components in parts by weight:
200 parts of D110 white oil (oily solvent) in a Qilu petrochemical refinery, 13.1 parts of span 80 emulsifier, 6.9 parts of isomeric tridecanol polyoxyethylene ether 1307 emulsifier, 1 part of hydrophobic silica (suspending agent) and 5 parts of dioctyl sodium sulfosuccinate (penetrating agent);
the process treating agent comprises the following components in parts by weight:
0.02 part of azodiisobutyl imidazoline hydrochloride, 0.02 part of potassium persulfate, 0.1 part of sodium bisulfite, 16 parts of sodium hydroxide (a hydrolytic agent) and 25 parts of fatty alcohol-polyoxyethylene ether (a phase transfer agent).
The preparation method of the low-temperature-resistant online adhesion promoter in the embodiment is prepared by adopting the composition for preparing the low-temperature-resistant online adhesion promoter, and comprises the following steps:
uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, N-methylenebisacrylamide and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, adding sodium chloride into the second mixed solution, fully dissolving, and then repeatedly measuring to ensure that the pH value is 7.0 to obtain an aqueous phase solution;
② mixing D110 white oil from the Qilu petrochemical Shengli oil refinery, span 80 emulsifier, isomeric tridecanol polyoxyethylene ether 1307 emulsifier, dioctyl sodium sulfosuccinate and hydrophobic silica at a stirring speed of 1500rpm until the hydrophobic silica is uniformly dispersed to obtain an oil phase solution;
③ adding the water phase solution, the azobisisobutyrimidazoline hydrochloride and the potassium persulfate into the oil phase solution at a uniform speed within 15 minutes at a stirring speed of 1500rpm to obtain an emulsion solution of uniform emulsion;
adjusting the system temperature of the emulsion solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping sodium bisulfite at a stirring speed of 500rpm to initiate polymerization, adding 30 wt.% of N-octadecyl acrylamide (namely adding 1.5 parts of N-octadecyl acrylamide) into the system after initiating polymerization, adding 30 wt.% of N-octadecyl acrylamide (namely adding 1.5 parts of N-octadecyl acrylamide) after reacting for 1h at the temperature of 35 ℃, adding the remaining 40 wt.% of N-octadecyl acrylamide (namely adding 2 parts of N-octadecyl acrylamide) after reacting for 1.5h at the temperature of 45 ℃, controlling the polymerization temperature at 60 ℃, and finishing the reaction after continuously reacting for 2h to obtain a polymerization emulsion;
after the reaction is finished, adding sodium hydroxide (a hydrolytic agent) into the polymerized emulsion at the stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
sixthly, after the heat preservation is finished, cooling the heat preservation treatment liquid to 30 ℃, adding fatty alcohol-polyoxyethylene ether at the stirring speed of 800rpm, and continuously stirring for 2 hours to obtain brown yellow liquid serving as the low-temperature-resistant online viscosity changing agent.
Example 2
The composition for preparing the low temperature resistant on-line viscosity modifier in this example consists of a dispersed water phase, a continuous oil phase and a process treatment agent;
the dispersed water phase comprises the following components in parts by weight:
125 parts of acrylamide, 175 parts of 2-acrylamido-2-methylpropanesulfonic acid, 50 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 8 parts of methacrylamidogetanol polyoxyethylene ether (long-chain flexible monomer), 33.5 parts of sodium hydroxide, 0.1 part of pentaerythritol triallyl ether (structure regulator), 65 parts of sodium acetate (pour point depressant) and 260 parts of water;
the continuous oil phase comprises the following components in parts by weight:
230 parts of D110 white oil (oily solvent) in a Qilu petrochemical refinery, 12.6 parts of cetearyl alcohol polyoxyethylene ether-10 emulsifier, 17.4 parts of propylene glycol block polyether L61 emulsifier, 3 parts of modified bentonite (suspending agent) and 7 parts of fatty alcohol polyoxyethylene ether JFC-U (penetrating agent);
the process treating agent comprises the following components in parts by weight:
0.03 part of azodiisobutyl imidazoline hydrochloride, 0.03 part of potassium persulfate, 0.1 part of sodium bisulfite, 24 parts of potassium hydroxide (a hydrolytic agent) and 30 parts of nonylphenol polyoxyethylene ether (a phase transfer agent).
The preparation method of the low-temperature-resistant online adhesion promoter in the embodiment is prepared by adopting the composition for preparing the low-temperature-resistant online adhesion promoter, and comprises the following steps:
uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, pentaerythritol triallyl ether and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, adding sodium acetate into the second mixed solution, fully dissolving, and then repeatedly measuring to ensure that the pH value is 7.0 to obtain an aqueous phase solution;
② under the stirring speed of 1500rpm, mixing the white oil D110 in the Qilu petrochemical Shengli oil refinery, the cetearyl alcohol polyoxyethylene ether-10 emulsifier, the propylene glycol block polyether L61 emulsifier, the modified bentonite and the fatty alcohol polyoxyethylene ether JFC-U until the modified bentonite is dispersed uniformly to obtain an oil phase solution;
③ adding the water phase solution, the azobisisobutyrimidazoline hydrochloride and the potassium persulfate into the oil phase solution at a uniform speed within 15 minutes at a stirring speed of 1500rpm to obtain an emulsion solution of uniform emulsion;
adjusting the system temperature of the emulsion solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping sodium bisulfite at a stirring speed of 500rpm to initiate polymerization, adding 30 wt.% of methacrylamide octadecanol polyoxyethylene ether (namely adding 2.4 parts of methacrylamide octadecanol polyoxyethylene ether) into the system after the initiation polymerization, adding 30 wt.% of methacrylamide octadecanol polyoxyethylene ether (namely adding 2.4 parts of methacrylamide octadecanol polyoxyethylene ether) after reacting for 1 hour at the temperature of 35 ℃, adding the remaining 40 wt.% of methacrylamide octadecanol polyoxyethylene ether (namely adding 3.2 parts of methacrylamide octadecanol polyoxyethylene ether) after reacting for 1.5 hours at the temperature of 45 ℃, controlling the polymerization temperature to 60 ℃, and finishing the reaction after continuously reacting for 2 hours to obtain a polymerization emulsion;
after the reaction is finished, adding potassium hydroxide (a hydrolytic agent) into the polymerized emulsion at the stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
sixthly, after the heat preservation is finished, cooling the heat preservation treatment liquid to 30 ℃, adding nonylphenol polyoxyethylene ether at the stirring speed of 800rpm, and continuously stirring for 2 hours to obtain brown yellow liquid serving as the low-temperature online viscosity changing agent.
Example 3
The composition for preparing the low temperature resistant on-line viscosity modifier in this example consists of a dispersed water phase, a continuous oil phase and a process treatment agent;
the dispersed water phase comprises the following components in parts by weight:
150 parts of acrylamide, 200 parts of 2-acrylamido-2-methylpropanesulfonic acid, 60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 10 parts of octadecyl acrylate (long-chain flexible monomer), 38 parts of sodium hydroxide, 0.2 part of pentaerythritol triallyl ether (structure regulator), 40 parts of sodium acetate (pour point depressant), 40 parts of sodium chloride and 330 parts of water;
the continuous oil phase comprises the following components in parts by weight:
260 parts of white oil (oily solvent) D110 in a Qilu petrochemical petroleum refinery, 13 parts of a span 80 emulsifier, 5 parts of an isomeric tridecanol polyoxyethylene ether 1303 emulsifier, 7 parts of a Tween 60 emulsifier, 7 parts of a castor oil polyoxyethylene ether EL-10 emulsifier, 5 parts of modified hectorite (a suspending agent) and 10 parts of isooctanol polyoxyethylene ether JFC-E (a penetrating agent).
The process treating agent comprises the following components in parts by weight:
0.03 part of azodiisobutyl imidazoline hydrochloride, 0.03 part of potassium persulfate, 0.1 part of sodium bisulfite, 33 parts of potassium hydroxide (a hydrolytic agent) and 5 parts of nonylphenol polyoxyethylene ether (a phase transfer agent).
The preparation method of the low-temperature-resistant online adhesion promoter in the embodiment is prepared by adopting the composition for preparing the low-temperature-resistant online adhesion promoter, and comprises the following steps:
uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, pentaerythritol triallyl ether and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, adding sodium acetate and sodium chloride into the second mixed solution, fully dissolving, and then repeatedly measuring to ensure that the pH value is 7.0 to obtain an aqueous phase solution;
② under the stirring speed of 1500rpm, mixing the white oil of the Qilu petrochemical Shengli oil refinery D110, the span 80 emulsifier, the isomeric tridecanol polyoxyethylene ether 1303 emulsifier, the Tween 60 emulsifier, the castor oil polyoxyethylene ether EL-10 emulsifier, the modified hectorite and the isooctanol polyoxyethylene ether JFC-E until the modified hectorite is dispersed evenly to obtain an oil phase solution;
③ adding the water phase solution, the azobisisobutyrimidazoline hydrochloride and the potassium persulfate into the oil phase solution at a uniform speed within 15 minutes at a stirring speed of 1500rpm to obtain an emulsion solution of uniform emulsion;
adjusting the system temperature of the milky solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping sodium bisulfite at a stirring speed of 500rpm to initiate polymerization, adding 30 wt.% of octadecyl acrylate (namely adding 3 parts of octadecyl acrylate) into the system after the initiation polymerization, adding 30 wt.% of octadecyl acrylate (namely adding 3 parts of octadecyl acrylate) after reacting for 1h at the temperature of 35 ℃, adding the remaining 40 wt.% of octadecyl acrylate (namely adding 4 parts of octadecyl acrylate) after reacting for 1.5h at the temperature of 45 ℃, controlling the polymerization temperature at 60 ℃, and finishing the reaction after continuously reacting for 2h to obtain a polymerization emulsion;
after the reaction is finished, adding potassium hydroxide (a hydrolytic agent) into the polymerized emulsion at the stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
sixthly, after the heat preservation is finished, cooling the heat preservation treatment liquid to 30 ℃, adding nonylphenol polyoxyethylene ether at the stirring speed of 800rpm, and continuously stirring for 2 hours to obtain brown yellow liquid serving as the low-temperature online viscosity changing agent.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online adhesion promoter does not contain a long-chain flexible monomer (N-octadecyl acrylamide):
in the first step, a long-chain flexible monomer (N-octadecyl acrylamide) is not added, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methacryloxyethyl-N, N-dimethylpropanesulfonate, N-methylene bisacrylamide and water are uniformly mixed to obtain a first mixed solution, then sodium hydroxide is added into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, sodium acetate is added into the second mixed solution, and after the sodium hydroxide is fully dissolved, the pH value is measured again and is made to be 7.0 to obtain an aqueous phase solution;
in the step (iv), no long-chain flexible monomer (N-octadecyl acrylamide) is added, that is, the step (iv) is: adjusting the system temperature of the emulsion solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping sodium bisulfite at the stirring speed of 500rpm to initiate polymerization, controlling the temperature at 45 ℃ to continuously perform polymerization reaction for 2.5h, controlling the temperature of the polymerization reaction at 60 ℃ to continuously perform polymerization reaction for 2h, and obtaining the polymerization emulsion after the reaction is finished.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
in the step IV, the system temperature of the emulsion solution is adjusted to 25 ℃, nitrogen is introduced to remove oxygen for 30min, sodium bisulfite is pumped in at the stirring speed of 500rpm to initiate polymerization, 5 parts of N-octadecyl acrylamide is directly added into the system after the initiation of polymerization, then the polymerization temperature is controlled at 45 ℃ for continuous polymerization for 2.5h, then the polymerization temperature is controlled at 60 ℃ for continuous polymerization for 2h, and the polymerization emulsion is obtained after the reaction is finished.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online adhesion promoter does not contain 2-acrylamide-2-methylpropanesulfonic acid, methacryloxyethyl-N, N-dimethylpropanesulfonate and a structure regulator (N, N-methylene bisacrylamide); the preparation method comprises the following steps of not adding 2-acrylamide-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethyl propanesulfonate and a structure regulator (N, N-methylene bisacrylamide) in the preparation step of the low-temperature-resistant online adhesion agent, uniformly mixing acrylamide and water in the step of mixing to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 7.0 to obtain a second mixed solution, adding sodium acetate into the second mixed solution, fully dissolving, and then testing again to enable the pH value to be 7.0 to obtain an aqueous phase solution.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online viscosity-changing agent does not contain a pour point depressant (sodium chloride); the adopted white oil is conventional No. 5 white oil (the freezing point is about 10 ℃); the preparation step of the low-temperature-resistant online viscosity modifier is that no pour point depressant (sodium chloride) is added, and the white oil adopted in the step II is conventional No. 5 white oil (the freezing point is about 10 ℃).
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that:
the composition for preparing the low temperature resistant on-line adhesion promoter does not contain a suspending agent (hydrophobic silica); no suspending agent (hydrophobic silicon dioxide) is added in the preparation step of the low-temperature-resistant online adhesion promoter.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online adhesion promoter does not contain a penetrating agent (dioctyl sodium sulfosuccinate) and does not contain a long-chain flexible monomer (N-octadecyl acrylamide); no penetrating agent (dioctyl sodium sulfosuccinate) is added in the preparation step of the low-temperature-resistant online adhesion promoter, and no long-chain flexible monomer (N-octadecyl acrylamide) is added in the step (iv).
Comparative example 7
Comparative example 7 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online adhesion promoter does not contain a hydrolytic agent (sodium hydroxide); directly carrying out heat preservation treatment for 4 hours without adding a hydrolytic agent (sodium hydroxide) in the preparation step (the fifth step) of the low temperature resistant on-line viscosity changing agent to obtain heat preservation treatment liquid.
The low-temperature-resistant online adhesion promoter prepared according to the embodiment and the comparative example is subjected to performance test, and the performance test results are shown in table 1.
The detection indexes and the detection method of the invention are as follows:
(1) drag reduction ratio: the test was carried out according to the method specified in NB/T14003.1-2015 at 7.8.
(2) Apparent viscosity: the polymer solution with the concentration of 8 per mill is prepared by tap water and the KCl solution with the concentration of 5 per mill respectively, the mixture is stirred for 5 minutes under the condition of 1000r/min of a vertical stirrer, and the viscosity of the polymer solution is measured by a six-speed viscometer at 100 revolutions.
(3) The sedimentation rate: and taking 100mL of the prepared 8 per mill polymer solution, adding 20-40% of ceramsite sand into a glass cup according to the sand ratio of 30%, uniformly stirring, pouring into a 100mL measuring cylinder, observing and recording the percentage of the settled height of the ceramsite sand to the total height of the sand carrying liquid, and calculating the ratio of 24h as the sand settling rate (namely the settling rate).
(4) Temperature resistance and shear resistance: a polymer solution with a concentration of 8 per mill was prepared from tap water, and the rheological properties of the drag reducer solution were tested using a model HAAKE MARS 40 rheometer. Wherein the shear rate is controlled at 170s-1The temperature is controlled at 90 ℃, the shearing time is 60 minutes, and the temperature resistance and the shearing resistance of the polymer solution are judged by taking the average value of the viscosity in the last 5 minutes.
Figure BDA0003003263280000221
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A composition for preparing a low temperature on-line tack-reducing agent, the composition comprising a dispersed aqueous phase, a continuous oil phase, and a process treatment;
the dispersed water phase comprises the following components in parts by weight:
100-150 parts of acrylamide, 150-200 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40-60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5-10 parts of long-chain flexible monomer, 29-38 parts of sodium hydroxide, 0.05-0.2 part of structure regulator, 50-80 parts of pour point depressant and 200-330 parts of water;
the continuous oil phase comprises the following components in parts by weight:
180-260 parts of an oily solvent, 20-40 parts of an emulsifier, 1-5 parts of a suspending agent and 5-10 parts of a penetrating agent;
the process treating agent comprises the following components in parts by weight:
0.02-0.5 part of initiator, 16-33 parts of hydrolytic agent and 25-35 parts of phase inversion agent.
2. The composition of claim 1, wherein:
the long-chain flexible monomer is one or more of N-octadecyl acrylamide, octadecyl acrylate and methacrylamide octadecanol polyoxyethylene ether;
the structure regulator is N, N-methylene bisacrylamide and/or pentaerythritol triallyl ether; and/or
The pour point depressant is one or more of sodium chloride, sodium acetate and ethylene glycol.
3. The composition of claim 1, wherein:
the oily solvent is one or more of kerosene, diesel oil, aviation kerosene, mineral oil and white oil, and preferably, the oily solvent is low-temperature-resistant white oil with the freezing point lower than-30 ℃;
the emulsifier is one or more of span 80, cetearyl alcohol polyoxyethylene ether-10, isomeric tridecanol polyoxyethylene ether 1303, isomeric tridecanol polyoxyethylene ether 1305, isomeric tridecanol polyoxyethylene ether 1307, isomeric tridecanol polyoxyethylene ether 1309, propylene glycol block polyether L61, propylene glycol block polyether L31, propylene glycol block polyether L42, propylene glycol block polyether L63, Tween 60, castor oil polyoxyethylene ether EL-10, castor oil polyoxyethylene ether EL-20 and castor oil polyoxyethylene ether EL-30; and/or
The water-oil balance value of the emulsifier is 6-8.
4. The composition of claim 1, wherein:
the suspending agent is one or more of hydrophobic silicon dioxide, modified bentonite and modified hectorite; and/or
The penetrating agent is one or more of dioctyl sodium sulfosuccinate, fatty alcohol-polyoxyethylene ether JFC-U and isooctanol-polyoxyethylene ether JFC-E.
5. The composition of claim 1, wherein:
the initiator is a composite initiation system, and the composite initiation system comprises an azo initiator, an oxidant and a reducing agent; the azo initiator is one or more of azobisisobutyramidine dihydrochloride, azobisisoheptonitrile and azobisisobutyrimidazoline hydrochloride, the oxidizing agent is potassium persulfate, and the reducing agent is sodium bisulfite;
the hydrolytic agent is one or more of sodium hydroxide, potassium hydroxide and sodium bicarbonate; and/or
The phase inversion agent is fatty alcohol polyoxyethylene ether and/or nonylphenol polyoxyethylene ether.
6. A method for preparing a low temperature-resistant online adhesion promoter, which is characterized in that the low temperature-resistant online adhesion promoter is prepared by using the composition for preparing the low temperature-resistant online adhesion promoter, which is disclosed by any one of claims 1 to 5, and the preparation method comprises the following steps:
(a) uniformly mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate, a structure regulator and water to obtain a first mixed solution, adding sodium hydroxide into the first mixed solution to adjust the pH value of the first mixed solution to 6.5-7.5 to obtain a second mixed solution, adding a pour point depressant into the second mixed solution, and fully dissolving the pour point depressant in the second mixed solution to obtain an aqueous phase solution;
(b) uniformly mixing an oily solvent, an emulsifier, a suspending agent and a penetrating agent to obtain an oil phase solution;
(c) adding the water phase solution, the azo initiator and the oxidant into the oil phase solution and uniformly mixing to obtain an emulsion solution;
(d) adjusting the temperature of the emulsion solution to 10-25 ℃, introducing nitrogen to remove oxygen, adding a reducing agent to initiate polymerization, and adding a long-chain flexible monomer to perform polymerization in the polymerization process to obtain a polymerization emulsion;
(e) adding a hydrolytic agent into the polymerized emulsion for heat preservation treatment to obtain heat preservation treatment liquid;
(f) and cooling the heat preservation treatment liquid to 20-30 ℃, adding a phase inversion agent into the heat preservation treatment liquid, and uniformly stirring to obtain the low-temperature-resistant online adhesion promoter.
7. The method of claim 6, wherein:
in the polymerization reaction process, the long-chain flexible monomer is divided into three parts and sequentially added, and the adding mode is as follows: adding a first part of long-chain flexible monomers for polymerization reaction after initiating polymerization reaction, adding a second part of long-chain flexible monomers for polymerization reaction after reacting for 1h, and adding a third part of long-chain flexible monomers for polymerization reaction after reacting for 1.5h to obtain polymerization emulsion.
8. The method of claim 7, wherein:
the first part of long-chain flexible monomers and the second part of long-chain flexible monomers are both 30 wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40 wt.% of the total amount of the long-chain flexible monomers; and/or
And continuing to perform polymerization reaction for 1.5-2.5 hours at the temperature of 60-65 ℃ after the third part of the long-chain flexible monomer is added.
9. The production method according to any one of claims 6 to 8, characterized in that:
in the step (b), uniformly mixing an oily solvent, an emulsifier, an auxiliary emulsifier and a penetrant at a stirring speed of 800-2000 rpm;
in the step (c), adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes at a stirring speed of 1000-2000 rpm to obtain the emulsion solution;
in the step (d), adding a reducing agent into the emulsion solution at a stirring speed of 200-500 rpm to initiate polymerization;
in the step (e), the temperature of the heat preservation treatment is 60-65 ℃, and the time of the heat preservation treatment is 3-6 hours; and/or
In the step (f), adding the phase transfer agent into the polymerization emulsion at a stirring speed of 500-1000 rpm, and stirring for 2-3 hours to obtain the low-temperature-resistant online adhesion promoter.
10. The low temperature-resistant in-line tackiness agent produced by the production method described in any one of claims 6 to 9.
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