CN113801267A - Thermosensitive polymer nano-microsphere for profile control and flooding and preparation method thereof - Google Patents
Thermosensitive polymer nano-microsphere for profile control and flooding and preparation method thereof Download PDFInfo
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- CN113801267A CN113801267A CN202111118769.XA CN202111118769A CN113801267A CN 113801267 A CN113801267 A CN 113801267A CN 202111118769 A CN202111118769 A CN 202111118769A CN 113801267 A CN113801267 A CN 113801267A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 59
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims abstract description 11
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002776 aggregation Effects 0.000 claims abstract description 4
- 238000004220 aggregation Methods 0.000 claims abstract description 3
- 230000004043 responsiveness Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 3
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000007872 degassing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 229920000208 temperature-responsive polymer Polymers 0.000 claims 3
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 239000012530 fluid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008363 phosphate buffer Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 tBAM Chemical compound 0.000 description 1
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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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
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- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention provides a thermo-sensitive polymer nano microsphere for deep profile control and flooding and a preparation method thereof, belonging to the technical field of new chemical materials and oil-gas field exploitation. The microsphere is mainly prepared by copolymerizing a temperature-sensitive monomer N-vinyl caprolactam, a hydrophobic monomer N-tert-butyl acrylamide and acrylic acid. The microspheres exist in water as VPTT (volume phase transition temperature). When the temperature is lower than VPTT, the microspheres are stably dispersed in the aqueous solution in a nanoscale, and the dispersion system is low in viscosity and high in stability; when the temperature is near VPTT, the polymer is precipitated from the aqueous solution in a nanoscale form, and the viscosity of the dispersion system is increased; when the temperature is continuously increased to be higher than VPTT, the separated nano-scale microspheres are aggregated and are precipitated and separated from the dispersion system in a micron-scale form. The raw materials are easy to obtain, the preparation process is simple, and the yield is more than 99.6%. The size and the aggregation state of the microsphere have temperature responsiveness, the viscosity of a dispersion system of the microsphere is reversely increased along with the rise of temperature, and the microsphere has a certain application value in the field of deep profile control of oil reservoirs in the middle and later periods of exploitation.
Description
Technical Field
The cross field of new chemical materials and oil-gas field exploitation technologies, in particular to a thermo-sensitive polymer nano microsphere for profile control and flooding and a preparation method thereof.
Background
The oil yield of the land middle-high permeability sandstone oil reservoir is 6311 multiplied by 104t/a, accounting for 33.0% of domestic production, is mainly used in old oil fields in the middle-late stage of development. Along with the use of various production increasing measures in long-term exploitation, the heterogeneity of an oil reservoir stratum is intensified, and injected water flows along a dominant channel. The water content of the produced liquid is greatly increased, and the unused crude oil accounts for 40 percent of the reserves. The starting of the residual oil of the medium-low permeability layer is a main problem to be solved in each large oil field.
The deep profile control and flooding method realizes the diversion of liquid flow by means of continuous redistribution of the profile control agent in the deep part of the stratum, improves the sweep efficiency of the displacement fluid, and is an effective means for stabilizing oil and controlling water. The polymer microsphere has small dosage, good dispersibility, controllable particle size and crosslinking without being influenced by stratum environment, and is a novel deep profile control and flooding technology developed in recent years. The gel microspheres are adsorbed on the rock surface, so that the water-phase permeability can be reduced; the hydration expansion can block the pore throat and can be transferred to the deep part under high pressure through deformation, so that the gradual blocking is realized. Dai Caili et al[[i]]Establishing a matching relation model of the gel particle size and the pore throat of the oil reservoir; mahmoud o[[ii]]Weak gel particles of small size were found to have better compressibility and a greater drag coefficient; guang Zhao[[iii]]The gel particles were found to have good selectivity for pore throat plugging.
When the temperature is lower than the gel transformation point, the dispersion system is low-viscosity fluid, the gel microspheres are uniformly and stably dispersed in water with high salinity in a nanoscale, and the temperature-sensitive reversible nano gel microspheres have good injection performance and small fluid resistance; when the temperature is increased to the gel transition point, the gel microspheres undergo hydrophilic-hydrophobic transition, the viscosity of the system begins to increase, and the system is still a nano-scale thermodynamically stable dispersion system, so that the oil displacement effect can be enhanced. When the temperature is further increased to be higher than the gel transition point, the nanogel microspheres are agglomerated and precipitate from the dispersion system in the form of micron-scale aggregates, so that the pore throats are blocked. The system has certain application value in the deep profile control and flooding field of oil fields in the middle and later periods of exploitation.
Disclosure of Invention
The invention provides a thermo-sensitive polymer nano microsphere for deep profile control and flooding and a preparation method thereof. The polymer nano-microsphere is mainly prepared by copolymerizing a temperature-sensitive monomer N-vinyl caprolactam (NVCL), a hydrophobic monomer N-tert-butyl acrylamide (tBA) and acrylic acid (AAc). The polymer nano-microsphere exists VPTT (volume phase transition temperature) in water. With the increase of the temperature, the nanometer microsphere has three morphological changes in the water solution. When the temperature is lower than the nano microsphere transformation point, the dispersion system is low-viscosity fluid, the microspheres are uniformly and stably dispersed in water with high mineralization degree in a nano scale, and the nano microsphere has good injection performance and small fluid resistance; when the temperature is increased to the gel transition point, the nano microspheres undergo hydrophilic-hydrophobic transition, the viscosity of the system begins to increase, and the nano microspheres are still a nano-scale thermodynamically stable dispersion system, so that the oil displacement effect can be enhanced. When the temperature is further increased to be higher than the transition point of the nano microspheres, the nano microspheres are agglomerated and precipitate from the dispersion system in the form of micron-scale aggregates, so that the pore throats are blocked. In order to achieve the above object, the present invention adopts the following technical solutions: dissolving NVCL, tBAM, AAc and a cross-linking agent in deionized water according to the calculated feed ratio to obtain a monomer mixed solution; then putting the monomer mixed solution into a glass reactor; adjusting the pH value of the system, introducing nitrogen, degassing and sealing; heating the mixed solution to a reaction temperature, and adding an initiator into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers.
The invention has the advantages of
(1) The nano microsphere has easily obtained raw materials, simple preparation process and yield of over 99.6 percent. The size and the aggregation state of the polymer microsphere have temperature responsiveness, the viscosity of a dispersion system of the polymer microsphere is reversely increased along with the rise of temperature, and the polymer microsphere has a certain application value in the field of deep profile control of oil reservoirs in the middle and later periods of exploitation.
(2) The nanometer microsphere is changed in three forms in sequence in the water solution, when the temperature is lower than the nanometer microsphere transformation point, the dispersion system is low-viscosity fluid, the microsphere is uniformly and stably dispersed in water with high mineralization degree in a nanometer scale, the injection performance is good, and the fluid resistance is small; when the temperature is increased to the gel transition point, the nano microspheres undergo hydrophilic-hydrophobic transition, the viscosity of the system begins to increase, and the nano microspheres are still a nano-scale thermodynamically stable dispersion system, so that the oil displacement effect can be enhanced. When the temperature is further increased to be higher than the transition point of the nano microspheres, the nano microspheres are agglomerated and precipitate from the dispersion system in the form of micron-scale aggregates, so that the pore throats are blocked.
Drawings
FIG. 1 is a FT-IR spectrum of a thermo-sensitive polymer nano-microsphere for profile control and flooding; FIG. 2 shows temperature-sensitive polymer nano-microspheres for profile control and flooding1H NMR spectrum; FIG. 3 shows the micro-morphology of thermo-sensitive polymer nanospheres for profile control; FIG. 4 is a schematic diagram of a phase transition process of the thermosensitive polymer nano-microsphere under the action of temperature.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the technical solutions of the present invention will be described in detail below, but the present invention is not limited to the technical features, the objects and the advantages.
Example 1
Dissolving 0.352 g of NVCL, 0.083 g of tBAM and 0.01 g N, N' -methylene bisacrylamide in deionized water to obtain a monomer mixed solution; then putting the monomer mixed solution into a reaction container; using 1M NaHCO3Adjusting the pH value of the system to 6.5, introducing nitrogen, degassing and sealing; heating the mixed solution to 70 ℃, dissolving 0.02g of azobisisobutyronitrile into acetone, and adding the mixture into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers. The resulting microgel had a VPTT of about 24 ℃ and was isolated at 99.5% in 10 mM phosphate buffer at pH 5.
Example 2
Dissolving 0.330 g of NVCL, 0.083 g of tBAM, 0.011 mL of AAc and 0.01 g of ethylene glycol methacrylate in deionized water to obtain a mixed solution of monomers; then putting the monomer mixed solution into a reaction container; using 1M KHCO3The pH value of the system is adjusted to be 8.0, introducing nitrogen, degassing and sealing; heating the mixed solution to the reaction temperature, and adding 0.02g of potassium persulfate into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers. The microgel obtained had a VPTT of about 19 ℃ and could be isolated at 99.3% in 10 mM phosphate buffer at pH 5.
Example 3
Dissolving 0.240 g of NVCL, 0.165 g of tBAM, 0.11 mL of AAc and 0.012g of 1, 3-butanediol dimethacrylate in deionized water to obtain a monomer mixed solution; then putting the monomer mixed solution into a reaction container; with Na2HPO4Adjusting the pH value of the system to 7, introducing nitrogen, degassing and sealing; heating the mixed solution to the reaction temperature, and adding 0.02g of ammonium persulfate into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers. The resulting microgel had a VPTT of about 10 ℃ and could be isolated at 99.8% in 10 mM phosphate buffer at pH 5.
Example 4
Dissolving 0.217 g of NVCL, 0.165 g of tBAM, 0.022 mL of AAc and 0.013 g of bisphenol A dimethacrylate in deionized water to obtain a monomer mixed solution; then putting the monomer mixed solution into a reaction container; use 1M K2HPO4Adjusting the pH value of the system to 7, introducing nitrogen, degassing and sealing; heating the mixed solution to the reaction temperature, and adding 0.02g of azodicyano valeric acid into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers. The resulting microgel had a VPTT of about 12 ℃ and could be isolated at 99.6% in 10 mM phosphate buffer at pH 5.
Example 5
Dissolving 0.307 g of NVCL, 0.083 g of tBAM, 0.022 mL of AAc and 0.013 g of 1, 4-butanediol dimethacrylate in deionized water to obtain a monomer mixed solution; then putting the monomer mixed solution into a reaction container; use 1M K2HPO4Adjusting the pH value of the system to 7, introducing nitrogen, degassing and sealing; heating the mixed solution to the reaction temperature, and adding 0.02g of azodicyano valeric acid into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impuritiesAnd unreacted monomer. The resulting microgel had a VPTT of about 20 ℃ and could be isolated at 99.5% in 10 mM phosphate buffer at pH 5.
Example 6
Dissolving 0.307 g of NVCL, 0.083 g of tBAM, 0.022 mL of AAc and 0.013 g of 1, 4-butanediol dimethacrylate in deionized water to obtain a monomer mixed solution; then putting the monomer mixed solution into a reaction container; use 1M K2HPO4Adjusting the pH value of the system to 7, introducing nitrogen, degassing and sealing; heating the mixed solution to the reaction temperature, and adding 0.02g of azobisisobutyronitrile into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers. The resulting microgel had a VPTT of about 20 ℃ and could be isolated at 99.5% in 10 mM phosphate buffer at pH 5.
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.
[[i]]Dai C, Liu Y, Zou C, et al. Investigation on matching relationship between dispersed particle gel (DPG) and reservoir pore-throats for in-depth profile control[J]. Fuel, 2017, 207: 109-120.
[[ii]]Elsharafi M O, Bai B. Experimental work to determine the effect of load pressure on the gel pack permeability of strong and weak preformed particle gels[J]. Fuel, 2017, 188: 332-342.
[[iii]]Zhao G, You Q, Tao J, et al. Preparation and application of a novel phenolic resin dispersed particle gel for in-depth profile control in low permeability reservoirs[J]. Journal of Petroleum Science and Engineering, 2018, 161: 703-714.
Claims (9)
1. A temperature-sensitive polymer nano-microsphere for profile control and flooding and a preparation method thereof are characterized in that the polymer nano-microsphere has the following characteristics:
1) the main component of the polymer nano-microsphere is a copolymerization product of vinyl caprolactam, tert-butyl acrylamide, acrylic acid and a crosslinking agent;
2) the polymer nano-microsphere comprises 77-48: 20-40: 1-10: 2 of vinyl caprolactam, tert-butyl acrylamide, acrylic acid and a crosslinking agent;
3) the polymer nano-microspheres have the particle size of less than 200 nm when the temperature is lower than VPTT, and stably exist; agglomeration occurs in a hypersalinity aqueous solution at a temperature above VPTT, precipitating as aggregates with a particle size >1 μm;
4) the VPTT of the polymer nano-microsphere can be adjusted between 10 and 70 ℃.
2. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 1, comprising the following steps: dissolving NVCL, tBAM, AAc and a cross-linking agent in deionized water according to the calculated feed ratio to obtain a monomer mixed solution; then putting the monomer mixed solution into a glass reactor; adjusting the pH value of the system, introducing nitrogen, degassing and sealing; heating the mixed solution to a reaction temperature, and adding an initiator into the system; after the reaction is finished, the prepared microgel is dialyzed to remove impurities and unreacted monomers.
3. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the molar ratio of the N-vinyl caprolactam, the N-tert-butyl acrylamide, the acrylic acid and the crosslinking agent is 77-48: 20-40: 1-10: 2.
4. The temperature-sensitive polymer nano-microsphere profile control and flooding agent for profile control and flooding as claimed in claim 2, and the preparation method thereof, is characterized in that: and adjusting the pH value within the range of 5.0-8.0.
5. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the pH value is adjusted by using one or a mixture of more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium hydrogen phosphate and dipotassium hydrogen phosphate as a reagent.
6. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the reaction temperature is in the range of 50-90 ℃.
7. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the cross-linking agent is one or a mixture of more of N, N' -methylene bisacrylamide, ethylene glycol methacrylate, triethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate and bisphenol A dimethacrylate.
8. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the initiation is one or a mixture of more of potassium persulfate, ammonium persulfate, azobisisobutyronitrile and azobiscyanovaleric acid.
9. The temperature-sensitive polymer nano-microsphere for profile control and flooding and the preparation method thereof according to claim 2 are characterized in that: the size and the aggregation state of the polymer microsphere have temperature responsiveness, the viscosity of a dispersion system of the polymer microsphere is reversely increased along with the rise of temperature, and the polymer microsphere has a certain application value in the field of deep profile control of oil reservoirs in the middle and later periods of exploitation.
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