CN113004460B - 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

Info

Publication number
CN113004460B
CN113004460B CN202110355606.7A CN202110355606A CN113004460B CN 113004460 B CN113004460 B CN 113004460B CN 202110355606 A CN202110355606 A CN 202110355606A CN 113004460 B CN113004460 B CN 113004460B
Authority
CN
China
Prior art keywords
agent
parts
temperature
polyoxyethylene ether
long
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110355606.7A
Other languages
Chinese (zh)
Other versions
CN113004460A (en
Inventor
荣敏杰
孙建波
许永升
于庆华
荣帅帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Nuoer Biological Technology Co Ltd
Original Assignee
Shandong Nuoer Biological Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Nuoer Biological Technology Co Ltd filed Critical Shandong Nuoer Biological Technology Co Ltd
Priority to CN202110355606.7A priority Critical patent/CN113004460B/en
Publication of CN113004460A publication Critical patent/CN113004460A/en
Application granted granted Critical
Publication of CN113004460B publication Critical patent/CN113004460B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

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 changer; 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 increasing rate of the proportion of low permeability reserves in oil and gas exploration reserves has been increasing 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 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 in 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 oilfield 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-resistant and salt-resistant performances. However, the CN201811646387.2 patent application is 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 curing 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 viscosity agent 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 agent; the dispersed water phase comprises the following components in parts by weight: 100 to 150 portions of acrylamide, 150 to 200 portions of 2-acrylamide-2-methylpropanesulfonic acid, 40 to 60 portions of methacryloyloxyethyl-N, N-dimethyl propanesulfonate, 5 to 10 portions of long-chain flexible monomer, 29 to 38 portions of sodium hydroxide, 0.05 to 0.2 portion of structure regulator, 50 to 80 portions of pour point depressant and 200 to 330 portions of water; the continuous oil phase comprises the following components in parts by weight: 180-260 parts of oily solvent, 20-40 parts of emulsifier, 1-5 parts of suspending agent and 5-10 parts of 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 transfer 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, 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 carry out 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 transfer 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 30wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40wt.% of the total amount of the long-chain flexible monomers; and/or continuing the polymerization reaction for 1.5-2.5 h 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), under the stirring speed of 1000-2000 rpm, adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes 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 h; and/or in the step (f), adding the phase inversion agent into the polymerization emulsion at the stirring speed of 500-1000 rpm, and stirring for 2-3 h 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-changing agent disclosed by the invention 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 low in winter, and the emulsion polymer becomes solid and cannot flow after being too low in temperature, so that the construction difficulty is increased 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 thickener product which cannot be used as a drag reducer in CN201811646387.2, the low-temperature-resistant online viscosity-changing agent prepared by the invention is a water-in-oil emulsion product, can be used as the drag reducer and a thickener, is high in dissolving 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 test curve of the drag reduction performance of the low temperature resistant on-line viscosity changing agent in examples 1 to 3 of the present invention.
FIG. 2 is a rheological property test curve of the low temperature resistant on-line tackifier 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 should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. 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 to 150 parts of acrylamide (e.g., 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or 150 parts), 150 to 200 parts of 2-acrylamido-2-methylpropanesulfonic acid (e.g., 150, 155, 160, 165, 170, 175, 180, 185, 190, 195 or 200 parts), 40 to 60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate (e.g., 40, 45, 50, 55 or 60 parts), 5 to 10 parts of long-chain flexible monomer (e.g., 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 parts), 29 to 38 parts of sodium hydroxide (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), 0.05 to 0.2 part of structure modifier (e.g., 0.05, 0.08, 0.1, 0.12, 0.15, 0.18, or 0.2 part), 50 to 80 parts of pour point depressant (e.g., 50, 55, 60, 65, 70, 75, or 80 parts), 200 to 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 of oily solvent (such as 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255 or 260 parts), 20-40 parts of emulsifier (such as 20, 25, 30, 35 or 40 parts), 1-5 parts of suspending agent (such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 parts), 5-10 parts of penetrating agent (such as 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 parts); the process treating agent comprises the following components in parts by weight: 0.02-0.5 part (e.g., 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 an initiator, 16-33 parts (e.g., 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, or 33 parts) of a hydrolyzing agent, 25-35 parts (e.g., 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35 parts) of a phase inversion 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 methacryloyloxyethyl-N, N-dimethyl propane sulfonate can improve the temperature resistance and salt resistance of the prepared viscosity-variable polymer; the structure regulator and the long-chain flexible monomer can enable the molecular chains of the variable-viscosity polymer to generate micro-crosslinking and association space network structures, 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 capability 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 degree 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, 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, cetostearyl 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 a plurality of (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 (HLB) value of 6 to 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 requirements on the type of the hydrophobic silica, and the hydrophobic silica may be, for example, hydrophobic silica of WACKER HDK H20 manufactured by Wacker chemical (China) Co., 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 higher, the surface area is larger, and the adsorption force is stronger; 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 co-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 variable viscosity agent in a second aspect, the low-temperature-resistant online variable viscosity agent is prepared by adopting the composition for preparing the low-temperature-resistant online variable viscosity agent in the first aspect, the composition for preparing the low-temperature-resistant online variable viscosity agent is a raw material for preparing the low-temperature-resistant online variable viscosity agent, 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 be 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) and preferably 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 to avoid the problem that the pour point depressant is added in advance and can 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, for example, at a stirring speed of 1000 to 2000rpm, to obtain the milky 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 present invention, specifically, for example, the system temperature of the milky solution is adjusted to 25 ℃, nitrogen is introduced to remove oxygen for 30min, a reducing agent is pumped in at a stirring speed of 200 to 500rpm to initiate polymerization, after the initiation of polymerization, 30wt.% of the long-chain flexible monomer is added to the system, for example, after reacting at 35 ℃ for 1h, 30wt.% of the long-chain flexible monomer is added, for example, after reacting at 45 ℃ for 1.5h, the remaining 40wt.% of the long-chain flexible monomer is added, the polymerization temperature is controlled at 60 ℃, and the reaction is ended after continuing to react for 2h, 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 present invention, specifically, for example, a hydrolysis agent is added to the polymerization emulsion at a stirring speed of 500 to 1000rpm to perform a heat-insulating treatment for 4 hours to obtain a heat-insulating 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 which is a low-temperature-resistant online viscosity-changing agent; in the invention, the low-temperature-resistant online viscosity-changing agent is also marked as a low-temperature-resistant online fracturing fluid viscosity-changing agent; the low-temperature-resistant online variable viscosity 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 nanoparticles 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 to 150 portions of acrylamide, 150 to 200 portions of 2-acrylamido-2-methylpropanesulfonic acid, 40 to 60 portions of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5 to 10 portions of long-chain flexible monomer, 29 to 38 portions of sodium hydroxide, 0.05 to 0.2 portion of structure regulator, 50 to 80 portions of pour point depressant, 200 to 330 portions of water, 180 to 260 portions of oily solvent, 20 to 40 portions of emulsifier, 1 to 5 portions of suspending agent, 5 to 10 portions of penetrating agent, 0.02 to 0.5 portion of initiator, 16 to 33 portions of hydrolytic agent and 25 to 35 portions of phase transfer agent; in the present invention, when it is preferable that the long-chain flexible monomer is divided into three parts and sequentially added, the amount of the long-chain flexible monomer is 5 to 10 parts, which means the total 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 suspension 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 initiating polymerization reaction, adding a first part of long-chain flexible monomer to carry out polymerization reaction, for example, reacting at 35 ℃ for 1 hour, then adding a second part of long-chain flexible monomer to carry out polymerization reaction continuously, for example, reacting at 45 ℃ for 1.5 hours, then adding a third part of long-chain flexible monomer to carry out polymerization reaction continuously, 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 a polymer molecular chain and improve the capability of reducing the flow resistance of the polymer emulsion in a turbulent flow state; after the monomer is added, the 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 30wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40wt.% 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 is continued at a temperature of 60 to 65 ℃ for 1.5 to 2.5 hours (e.g., 1.5, 2, or 2.5 hours) after the addition of the third portion of the long chain flexible monomer.
According to some preferred embodiments, in step (b), the oily solvent, the emulsifier, the co-emulsifier and the penetrant are mixed uniformly at a stirring speed of 800-2000 rpm until the suspending agent is dispersed uniformly; in the step (c), under the stirring speed of 1000-2000 rpm, adding the water phase solution, the azo initiator and the oxidant into the oil phase solution at a uniform speed within 10-20 minutes 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 aqueous phase solution, the azo initiator and the oxidant are added into the oil phase solution at a uniform speed within 10 to 20 minutes to obtain the milky solution, so that emulsification can be 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 the stirring speed of 500-1000 rpm, and stirring for 2-3 h 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 the oily solvent, the emulsifier, the penetrating agent and the suspending agent at the 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 30wt.% of long-chain flexible monomer into the system after the initiation of polymerization, adding 30wt.% of long-chain flexible monomer after reacting for 1h, adding the remaining 40wt.% 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 polymerization emulsion at a stirring speed of 500-1000 rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
(f) 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 on-line tack-reducing agent produced by the production method described in the second aspect of the present invention.
The invention will be further described by way of example only, without the scope of protection of the invention being limited to these examples.
Example 1
The composition for preparing the low temperature resistant on-line viscosity changing agent in the embodiment 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:
(1) 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 in the Qilu petroleum and Shengli oil refinery, a span 80 emulsifier, an 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, azobisisobutylimidazoline hydrochloride and potassium persulfate into the oil phase solution at a uniform speed within 15 minutes at a stirring speed of 1500rpm to obtain a uniform emulsion milky solution;
(4) 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 30wt.% of N-octadecyl acrylamide (namely adding 1.5 parts of N-octadecyl acrylamide) into the system after initiating polymerization, adding 30wt.% of N-octadecyl acrylamide (namely adding 1.5 parts of N-octadecyl acrylamide) after reacting at 35 ℃ for 1h, adding the remaining 40wt.% of N-octadecyl acrylamide (namely adding 2 parts of N-octadecyl acrylamide) after reacting at 45 ℃ for 1.5h, controlling the polymerization temperature to be 60 ℃, and finishing the reaction after continuously reacting for 2h to obtain a polymerization emulsion;
(5) after the reaction is finished, adding sodium hydroxide (a hydrolytic agent) into the polymerization emulsion at a stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
(6) 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 azodiisobutylimidazoline 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:
(1) 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 measuring again to ensure that the pH value is 7.0 to obtain an aqueous phase solution;
(2) mixing D110 white oil, cetearyl alcohol polyoxyethylene ether-10 emulsifier, propylene glycol block polyether L61 emulsifier, modified bentonite and fatty alcohol polyoxyethylene ether JFC-U in a Qilu petrochemical refinery at a stirring speed of 1500rpm until the modified bentonite is uniformly dispersed to obtain an oil phase solution;
(3) adding the water phase solution, azobisisobutylimidazoline hydrochloride and potassium persulfate into the oil phase solution at a uniform speed within 15 minutes at a stirring speed of 1500rpm to obtain a uniform emulsion milky solution;
(4) 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 30wt.% of methacrylamidooctadecanol polyoxyethylene ether (namely adding 2.4 parts of methacrylamidooctadecanol polyoxyethylene ether) into the system after initiating polymerization, adding 30wt.% of methacrylamidooctadecanol polyoxyethylene ether (namely adding 2.4 parts of methacrylamidooctadecanol polyoxyethylene ether) after reacting for 1 hour at the temperature of 35 ℃, adding the remaining 40wt.% of methacrylamidooctadecanol polyoxyethylene ether (namely adding 3.2 parts of methacrylamidooctadecanol polyoxyethylene ether) after reacting for 1.5 hours at the temperature of 45 ℃, controlling the polymerization temperature to 60 ℃, and continuously reacting for 2 hours to obtain a polymerization emulsion after the reaction is finished;
(5) after the reaction is finished, adding potassium hydroxide (a hydrolytic agent) into the polymerization emulsion at a stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
(6) 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 a brown yellow liquid as the low-temperature on-line 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 azodiisobutylimidazoline 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:
(1) 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 measuring again 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, a span 80 emulsifier, an isomeric tridecanol polyoxyethylene ether 1303 emulsifier, a Tween 60 emulsifier, a castor oil polyoxyethylene ether EL-10 emulsifier, modified hectorite and isooctanol polyoxyethylene ether JFC-E at a stirring speed of 1500rpm until the modified hectorite 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 a uniform emulsion;
(4) 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 30wt.% of octadecyl acrylate (namely adding 3 parts of octadecyl acrylate) into the system after initiating polymerization, adding 30wt.% of octadecyl acrylate (namely adding 3 parts of octadecyl acrylate) after reacting for 1h at a temperature of 35 ℃, adding the remaining 40wt.% of octadecyl acrylate (namely adding 4 parts of octadecyl acrylate) after reacting for 1.5h at a temperature of 45 ℃, controlling the polymerization temperature at 60 ℃, and finishing the reaction after continuously reacting for 2h to obtain a polymerization emulsion;
(5) after the reaction is finished, adding potassium hydroxide (a hydrolytic agent) into the polymerization emulsion at a stirring speed of 800rpm for heat preservation treatment for 4 hours to obtain heat preservation treatment liquid;
(6) and 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 a brown yellow liquid serving as the low-temperature-resistant 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 step (1), a long-chain flexible monomer (N-octadecyl acrylamide) is not added, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methacryloxyethyl-N, N-dimethylpropanesulfonate, N-methylenebisacrylamide 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 second mixed solution is tested again to ensure that the pH value is 7.0 to obtain an aqueous phase solution;
in the step (4), the long-chain flexible monomer (N-octadecyl acrylamide) is not added, namely the step (4) is as follows: adjusting the system temperature of the milky solution to 25 ℃, introducing nitrogen to remove oxygen for 30min, pumping sodium bisulfite to initiate polymerization at a stirring speed of 500rpm, controlling the temperature at 45 ℃ to continuously carry out polymerization reaction for 2.5h, controlling the polymerization reaction temperature at 60 ℃ to continuously carry out 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 (4), 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 a 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 (1) not adding 2-acrylamide-2-methylpropanesulfonic acid, methacryloyloxyethyl-N, N-dimethylpropanesulfonate and a structure regulator (N, N-methylenebisacrylamide) in the preparation step of the low-temperature-resistant online variable viscosity agent, uniformly mixing acrylamide and water in the step (1) to obtain a first mixed solution, then 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, then adding sodium acetate into the second mixed solution, fully dissolving, and retesting to ensure that the pH value is 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 ℃); in the step (1) of preparing the low-temperature-resistant online viscosity modifier, no pour point depressant (sodium chloride) is added, and the white oil adopted in the step (2) 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); in the step (2) of preparing the low-temperature-resistant online viscosity-changing agent, a suspending agent (hydrophobic silicon dioxide) is not added.
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); in the step (2) of preparing the low-temperature-resistant online viscosity changer, a penetrating agent (dioctyl sodium sulfosuccinate) is not added, and in the step (4), a long-chain flexible monomer (N-octadecyl acrylamide) is not added.
Comparative example 7
Comparative example 7 is substantially the same as example 1 except that:
the composition for preparing the low-temperature-resistant online-variable adhesive does not contain a hydrolytic agent (sodium hydroxide); and (4) directly carrying out heat preservation treatment for 4 hours without adding a hydrolytic agent (sodium hydroxide) in the step (5) of preparing the low-temperature-resistant online 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: taking 100mL of the prepared 8 per mill polymer solution, adding 20-40 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 24 hours 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 with tap water, and the rheological properties of the drag reducer solution were tested using a HAAKE MARS 40 type rheometer. Wherein the shear rate is controlled at 170s -1 The 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 not limited thereto.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and 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 (7)

1. The preparation method of the low-temperature-resistant online variable viscosity agent is characterized in that the low-temperature-resistant online variable viscosity agent is prepared from a composition for preparing the low-temperature-resistant online variable viscosity agent, wherein the composition comprises 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 to 150 parts of acrylamide, 150 to 200 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40 to 60 parts of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, 5 to 10 parts of long-chain flexible monomer, 29 to 38 parts of sodium hydroxide, 0.05 to 0.2 part of structure regulator, 50 to 80 parts of pour point depressant and 200 to 330 parts of water; the long-chain flexible monomer is one or more of N-octadecyl acrylamide, octadecyl acrylate and methacrylamide octadecanol polyoxyethylene ether; the pour point depressant is one or more of sodium chloride, sodium acetate and ethylene glycol;
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 oily solvent is low-temperature resistant white oil with the freezing point lower than-30 ℃;
the process treating agent comprises the following components in parts by weight: 0.02 to 0.5 part of initiator, 16 to 33 parts of hydrolytic agent and 25 to 35 parts of phase transfer agent; the initiator is a composite initiation system, and the composite initiation system comprises an azo initiator, an oxidant and a reducing agent; the hydrolytic agent is one or more of sodium hydroxide, potassium hydroxide and sodium bicarbonate;
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 be 6.5 to 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 into 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 to 25 ℃, introducing nitrogen to remove oxygen, 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 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 monomer to carry out polymerization reaction after initiating polymerization reaction, adding a second part of long-chain flexible monomer to carry out polymerization reaction continuously after reacting for 1h at 35 ℃, adding a third part of long-chain flexible monomer to carry out polymerization reaction continuously for 1.5 to 2.5h at the temperature of 60 to 65 ℃ after reacting for 1.5h at 45 ℃, and obtaining polymerization emulsion; the first part of long-chain flexible monomers and the second part of long-chain flexible monomers are both 30wt.% of the total amount of the long-chain flexible monomers, and the third part of long-chain flexible monomers is 40wt.% of the total amount of the long-chain flexible monomers;
(e) Adding a hydrolytic agent into the polymerized emulsion for heat preservation treatment to obtain heat preservation treatment liquid; the temperature of the heat preservation treatment is 60 to 65 ℃, and the time of the heat preservation treatment is 3 to 6h;
(f) And (3) cooling the heat preservation treatment liquid to 20-30 ℃, adding a phase transfer agent into the heat preservation treatment liquid, and uniformly stirring to obtain the low-temperature-resistant online adhesion promoter.
2. The method of claim 1, wherein:
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 to 20 minutes at a stirring speed of 1000 to 2000rpm to obtain an emulsion solution;
in the step (d), adding a reducing agent into the emulsion solution at a stirring speed of 200 to 500rpm to initiate polymerization reaction; and/or
In the step (f), adding the phase transfer agent into the polymerization emulsion at a stirring speed of 500-1000rpm, and stirring for 2-3h to obtain the low-temperature-resistant online adhesion promoter.
3. The method of claim 1, wherein:
the structure regulator is N, N-methylene bisacrylamide and/or pentaerythritol triallyl ether.
4. The method of claim 1, wherein:
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 to 8.
5. The method 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.
6. The method of claim 1, wherein:
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; and/or
The phase inversion agent is fatty alcohol polyoxyethylene ether and/or nonylphenol polyoxyethylene ether.
7. The low temperature-resistant on-line tackiness agent produced by the production method described in any one of claims 1 to 6.
CN202110355606.7A 2021-04-01 2021-04-01 Low-temperature-resistant online viscosity-changing agent and preparation method thereof Active CN113004460B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110355606.7A CN113004460B (en) 2021-04-01 2021-04-01 Low-temperature-resistant online viscosity-changing agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110355606.7A CN113004460B (en) 2021-04-01 2021-04-01 Low-temperature-resistant online viscosity-changing agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113004460A CN113004460A (en) 2021-06-22
CN113004460B true CN113004460B (en) 2022-10-21

Family

ID=76387732

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110355606.7A Active CN113004460B (en) 2021-04-01 2021-04-01 Low-temperature-resistant online viscosity-changing agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113004460B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265025B (en) * 2021-07-21 2021-09-17 山东诺尔生物科技有限公司 Water-based high-molecular polymer suspension emulsion and preparation method thereof
CN113321766B (en) * 2021-08-03 2021-10-01 山东诺尔生物科技有限公司 Multi-element association type fracturing fluid thickening agent and preparation method thereof
CN113549442A (en) * 2021-08-30 2021-10-26 四川奥赛德材料科技有限公司 Functional composite thickening agent for integrated fracturing process
CN113789164A (en) * 2021-11-16 2021-12-14 中海油天津化工研究设计院有限公司 Multifunctional emulsion type thickening agent for fracturing and preparation method thereof
CN114316130B (en) * 2021-12-27 2023-04-25 爱森（中国）絮凝剂有限公司 Method for utilizing byproduct sodium chloride of industrial production dimethyl diallyl ammonium chloride in cationic emulsion
CN114560967B (en) * 2021-12-28 2023-03-31 爱森（中国）絮凝剂有限公司 Preparation method of low-temperature anti-freezing emulsion polymer thickening agent for fracturing

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103772601B (en) * 2012-10-24 2016-05-25 中国石油化工股份有限公司 A kind of acrylamide based copolymer and its preparation method and application
CN103951785B (en) * 2014-04-01 2016-03-09 中国石油天然气股份有限公司 A kind of fracturing liquid flow improver and its preparation method and application
CN105601840B (en) * 2016-01-21 2018-09-14 中国石油化工股份有限公司 A kind of acrylamide/sodium Acrylate multiple copolymer, preparation method and emulsion-type aqueous fracturing fluid drag reducer
CN111518239B (en) * 2020-06-19 2021-09-28 东营施普瑞石油工程技术有限公司 Emulsion type fracturing fluid resistance reducing agent and preparation method thereof
CN112521560B (en) * 2020-12-07 2023-05-30 西安长庆化工集团有限公司 Efficient salt-resistant one-dose dual-purpose thickening agent and preparation method and application thereof

Also Published As

Publication number Publication date
CN113004460A (en) 2021-06-22

Similar Documents

Publication Publication Date Title
CN113004460B (en) Low-temperature-resistant online viscosity-changing agent and preparation method thereof
CN108315003B (en) Polyacrylamide microsphere deep profile control and flooding agent and preparation method and application thereof
CN102304201B (en) Hydrophobic association crosslinked polymer coil and preparation method thereof
CN112521560A (en) Efficient salt-resistant one-agent dual-purpose thickening agent and preparation method and application thereof
US10047279B2 (en) High temperature viscoelastic surfactant (VES) fluids comprising polymeric viscosity modifiers
WO2016109348A1 (en) Emulsions containing alkyl ether sulfates and uses thereof
CN106350053A (en) Quick-dissolving type seawater-based high-temperature fracturing fluid
CN114940894B (en) Star-shaped temperature-resistant fracturing fluid thickening agent and preparation method thereof
CN111763511B (en) Preparation and liquid preparation method of integrated self-crosslinking thickener modified polymer for fracturing
CN112898484B (en) Oil-gas field plugging-regulating and flooding multifunctional medicament and preparation process thereof
CN113621106A (en) Multi-effect emulsion type thickening agent and preparation method thereof
CN114014994A (en) Resistance reducing agent capable of mixing and adjusting viscosity on line, resistance reducing type fracturing fluid and preparation method thereof
CN111423537A (en) Fracturing fluid stock solution and preparation method thereof, acidizing fracturing fluid, resistance reducing water and sand-carrying fracturing fluid
CN114805709B (en) Ultrahigh-temperature-resistant nano plugging agent with emulsion stability for oil-based drilling fluid and preparation method and application thereof
EP1285147A1 (en) Method of oil/gas well stimulation
CN114560967B (en) Preparation method of low-temperature anti-freezing emulsion polymer thickening agent for fracturing
CN117186288A (en) Drag reducer for oil reservoir acidizing and fracturing and preparation method thereof
CN108484827B (en) Emulsion with resistance reduction and thickening performance in fracturing and rapid dissolution and preparation method thereof
CN114686183B (en) Lubricating plugging filtrate reducer for drilling fluid and preparation method thereof
CN101240044B (en) Method for preparing cross-linking polymer clew with bimodal distribution grain diameter
CN113684016A (en) Super-salt-tolerant suspended slickwater resistance reducing agent and preparation method thereof
WO2019025810A1 (en) Crosslinked polymer microparticles for use in conformance control
CN111087553B (en) Multilayer core-shell structure polymer microsphere, profile control agent, preparation method and application thereof
CN111253925B (en) Application of thermal-tackifying emulsion polymer, and fracturing fluid sand carrier and slickwater drag reducer based on thermal-tackifying emulsion polymer
CN111393566A (en) Fracturing fluid emulsion stock solution, preparation method thereof, slick water and suspended sand fracturing fluid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A low-temperature resistant online viscosity changing agent and its preparation method

Effective date of registration: 20230904

Granted publication date: 20221021

Pledgee: Dongying Bank Co.,Ltd. Xianhe sub branch

Pledgor: SHANDONG NUOER BIOLOGICAL TECHNOLOGY Co.,Ltd.

Registration number: Y2023980055138

PE01 Entry into force of the registration of the contract for pledge of patent right