CN113634204B - Polymer microsphere capable of being subjected to secondary crosslinking and preparation method and application thereof - Google Patents
Polymer microsphere capable of being subjected to secondary crosslinking and preparation method and application thereof Download PDFInfo
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- CN113634204B CN113634204B CN202110914215.4A CN202110914215A CN113634204B CN 113634204 B CN113634204 B CN 113634204B CN 202110914215 A CN202110914215 A CN 202110914215A CN 113634204 B CN113634204 B CN 113634204B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 210
- 229920000642 polymer Polymers 0.000 title claims abstract description 197
- 238000004132 cross linking Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 108010010803 Gelatin Proteins 0.000 claims abstract description 66
- 229920000159 gelatin Polymers 0.000 claims abstract description 66
- 239000008273 gelatin Substances 0.000 claims abstract description 66
- 235000019322 gelatine Nutrition 0.000 claims abstract description 66
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 18
- 238000012688 inverse emulsion polymerization Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 31
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- -1 organic acid salt Chemical class 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- XFJRTXJMYXFAEE-UHFFFAOYSA-K [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O XFJRTXJMYXFAEE-UHFFFAOYSA-K 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000010690 paraffinic oil Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 abstract description 25
- 230000032683 aging Effects 0.000 description 53
- 238000009826 distribution Methods 0.000 description 24
- 238000000879 optical micrograph Methods 0.000 description 17
- 239000004576 sand Substances 0.000 description 14
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000008961 swelling Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 230000033558 biomineral tissue development Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000008398 formation water Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
-
- 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
-
- 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
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A polymer microsphere capable of being subjected to secondary crosslinking, a preparation method and application thereof, wherein the preparation method comprises the following steps: emulsifying gelatin in oil phase; adding metal salt into emulsified gelatin and solidifying the gelatin, so that the metal salt is coated inside the solidified gelatin to obtain the core of the polymer microsphere; coating a polymer shell on the outer part of the core by adopting an inverse emulsion polymerization method to obtain the polymer microsphere; the polymer microsphere is obtained by the preparation method. The polymer microsphere disclosed by the application can be subjected to secondary crosslinking, has better plugging capacity and oil displacement capacity, and can be used as a plugging agent or an oil displacement agent in oilfield exploitation.
Description
Technical Field
The application relates to the field of microsphere plugging, in particular to a polymer microsphere capable of being subjected to secondary crosslinking, and a preparation method and application thereof.
Background
The water content of the Bohai sea in the oil field production reaches 83%, the crude oil extraction degree reaches 17.5%, the whole oil field steps into a double-high stage, the difficulty of stabilizing the yield of the Bohai sea is greater and greater, and the requirement on water control and oil stabilization technology is also more and more prominent. With successful large-scale application of the oil-filled microsphere technology in the Bohai sea water injection field, the superiority of the technology is more and more prominent. At present, two main microsphere systems are mainly used in China: the particle size is increased by self water absorption expansion, the stratum is blocked by physical blocking, but the function is relatively single, and complex stratum conditions (such as high temperature, hypersalinity and the like) influence the stability of a system and destroy the internal molecular structure of the system, so that the system is difficult to perform deep profile control; the other is to realize the increase of particle size by self-cementing of a core-shell structure, and has good filling effect, but the change of injection pressure is relatively limited, and the plugging capability needs to be further improved so as to adapt to the plugging of the dominant seepage channel in the later development stage of the high-water-content oil field.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
The application provides a polymer microsphere, a preparation method and application thereof, wherein the polymer microsphere has better plugging capability and oil displacement capability, can be used as a plugging agent or an oil displacement agent in oilfield exploitation, has a simple preparation method and process, and can be used for preparing regular spherical polymer microspheres.
The application provides a preparation method of polymer microspheres capable of being subjected to secondary crosslinking, which comprises the following steps: emulsifying gelatin in oil phase;
adding metal salt into emulsified gelatin and solidifying the gelatin, so that the metal salt is coated inside the solidified gelatin to obtain the core of the polymer microsphere;
and coating a polymer shell on the outer part of the core by adopting an inverse emulsion polymerization method to obtain the polymer microsphere.
In an embodiment of the present application, the method for preparing the secondary cross-linkable polymer microsphere may include:
(1) Preparing the oil phase using an oil and a surfactant;
(2) Adding an aqueous solution of gelatin into the oil phase obtained in the step (1), and emulsifying the gelatin in the oil phase;
(3) Dropwise adding metal salt into the system obtained in the step (2), cooling to solidify the gelatin, and coating the metal salt in the solidified gelatin to obtain the core of the polymer microsphere;
(4) Mixing a monomer forming the polymer shell, a cross-linking agent and an oxidation initiator to form a mixed solution containing the monomer, adding the mixed solution containing the monomer into the system obtained in the step (3), and coating the mixed solution containing the monomer on the outer side of the core of the polymer microsphere;
(5) Adding a reduced initiator into the system obtained in the step (4), and performing inverse emulsion polymerization reaction on the reduced initiator and the monomer-containing mixed solution coated on the outer side of the core of the polymer microsphere, so that a polymer shell is coated on the outer side of the core of the polymer microsphere, thereby obtaining the polymer microsphere.
In an embodiment of the present application, in the step (3), the metal salt may be an organic acid salt of a metal selected from any one of chromium, zirconium and aluminum, and the organic acid may be selected from any one of acetic acid, citric acid and lactic acid.
In an embodiment of the present application, the metal salt may be selected from any one of chromium acetate, zirconium acetate, aluminum citrate, zirconium citrate, and chromium lactate.
In embodiments of the present application, the metal salt may comprise from 1.91% to 2.84% by mass of the total mass of the entire system in which the polymeric microspheres are prepared.
In embodiments of the application, the temperature may be reduced to below 10 ℃ and stirring continued until the gelatin solidifies.
Optionally, the duration of stirring may be from 15 minutes to 40 minutes.
In an embodiment of the present application, step (1) may include: mixing the oil and the surfactant, stirring and heating to a first temperature to obtain the oil phase.
In an embodiment of the present application, the oil may be selected from any one or more of white oil and paraffinic oil.
In embodiments of the present application, the surfactant may be selected from any one or more of Span80, OP-4, and Span-60.
In an embodiment of the present application, the first temperature may be 45 ℃ to 68 ℃.
In an embodiment of the present application, step (2) may include:
(2-1) adding an aqueous solution of gelatin to the oil phase obtained in step (1) and emulsifying the gelatin under stirring at a second temperature;
(2-2) cooling the system obtained in the step (2-1) and reducing the stirring speed, and continuing emulsifying the gelatin under the third temperature and stirring condition.
In an embodiment of the present application, in step (2-1), the second temperature may be 45 ℃ to 68 ℃; the speed of agitation may be 800 revolutions per minute to 1200 revolutions per minute; the gelatin emulsifying time may be 15 minutes to 40 minutes.
In embodiments of the application, the gelatin may comprise 1% to 3% of the total mass of the entire system in which the polymeric microspheres are prepared.
In an embodiment of the present application, in step (2-2), the third temperature may be 30 ℃ to 45 ℃; the stirring speed can be reduced to 500 to 800 rpm; the time for continuing emulsification of gelatin may be 1 hour or more.
In an embodiment of the present application, step (4) may include:
(4-1) mixing acrylic acid, acrylamide, a crosslinking agent, an oxidation initiator and water and adjusting the pH with a base to obtain the monomer-containing mixed solution;
(4-2) dropwise adding the monomer-containing mixed solution into the system obtained in the step (3), continuously stirring and introducing nitrogen gas, so that the monomer-containing mixed solution is coated on the outer side of the core of the polymer microsphere.
In an embodiment of the present application, in step (4-1), the crosslinking agent may be selected from any one or both of N, N-methylenebisacrylamide and divinylbenzene; the oxidation initiator can be selected from any one or two of potassium persulfate and ammonium persulfate; the base can be selected from any one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine; the pH can be adjusted to 5 to 8 with a base.
In an embodiment of the present application, in the step (4-1), the mass of the acrylic acid may account for 1.45% to 2.90% of the total mass of the entire system for preparing the polymer microsphere; the mass of the acrylamide may be 16.38% to 17.83% of the total mass of the entire system in which the polymer microsphere is prepared; the mass of the crosslinking agent may be less than 2% of the total mass of the entire system in which the polymeric microspheres are prepared; the mass of the oxidized initiator may be 0.025% to 1% of the total mass of the entire system in which the polymeric microspheres are prepared.
In an embodiment of the present application, in the step (4-2), the speed of the continuous stirring may be 500 rpm to 800 rpm.
In an embodiment of the present application, step (5) may include: and (3) adding the reduced initiator into the system obtained in the step (4), and controlling the temperature of the system at a fourth temperature to perform inverse emulsion polymerization reaction, so that the core of the polymer microsphere is coated with a polymer shell, thereby obtaining the polymer microsphere.
In embodiments of the application, the fourth temperature may not exceed 60 ℃; the reaction time of the inverse emulsion polymerization may be 1 hour to 2.5 hours.
In an embodiment of the present application, the reduced initiator may be selected from any one or more of an aqueous sodium bisulfite solution, an aqueous sodium sulfite solution, an aqueous ferrous sulfate solution, and N-N dimethylaniline.
In embodiments of the present application, the reduced initiator may comprise 0.025% to 1% by mass (based on the active ingredient) of the total mass of the entire system in which the polymeric microspheres are prepared.
The embodiment of the application also provides a polymer microsphere capable of being subjected to secondary crosslinking, which comprises a core and a shell coated outside the core, wherein the core comprises metal salt and gelatin coated outside the metal salt, and the shell is a polymer with a three-dimensional network structure.
In an embodiment of the present application, the metal salt may be an organic acid salt of a metal selected from any one of chromium, zirconium and aluminum, and the organic acid may be selected from any one of acetic acid, citric acid and lactic acid.
In an embodiment of the present application, the metal salt may be selected from any one of chromium acetate, zirconium acetate, aluminum citrate, zirconium citrate, and chromium lactate.
In embodiments of the present application, the housing may be a polymer formed from acrylic acid monomers, sodium acrylate monomers, and acrylamide monomers.
In an embodiment of the present application, the polymer microsphere may be obtained by the preparation method of the polymer microsphere capable of being secondarily crosslinked as described above.
In embodiments of the application, the average particle size of the polymeric microspheres may be 5 μm or less.
The embodiment of the application also provides the application of the polymer microsphere capable of being subjected to secondary crosslinking in oilfield exploitation as a plugging agent or an oil displacement agent.
The preparation method of the polymer microsphere takes the existing microsphere system as a functional carrier, coats the secondary crosslinking agent therein, and simultaneously controls the release and the action of the secondary crosslinking agent in the deep part of the stratum by means of an intelligent controlled release technology, thereby realizing the purpose of high-efficiency 'regulating-blocking' composite action.
The polymer microsphere is in a regular sphere shape, has small initial particle size and can penetrate into the deep part of an oil reservoir; under the action of the temperature and mineralization of stratum water, the polymer microsphere can be swelled, so that the pore diameter of the three-dimensional network structure of the shell is enlarged, the secondary crosslinking agent in the core is released, the released secondary crosslinking agent can be hydrolyzed to form polynuclear hydroxyl bridging ions, and the polynuclear hydroxyl bridging ions and the hydrolyzed carboxyl-containing polymer microsphere are subjected to secondary crosslinking to form a large secondary crosslinking body, so that the polymer microsphere prepared by the embodiment of the application has better plugging capability and oil displacement capability, and can be used as a plugging agent or an oil displacement agent in oilfield exploitation.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The accompanying drawings are included to provide an understanding of the principles of the application, and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain, without limitation, the principles of the application.
FIG. 1 is a graph showing the initial particle size distribution of polymer microspheres of example 1 of the present application;
FIG. 2 is a graph showing the initial particle size distribution of the polymer microspheres of example 1 of the present application after aging for 1 d;
FIG. 3 is a graph showing the initial particle size distribution of the polymer microspheres of example 1 of the present application after 3d aging;
FIG. 4 is a graph showing the initial particle size distribution of the polymer microspheres of example 1 of the present application after aging for 4 days;
FIG. 5 is a graph showing the initial particle size distribution of the polymer microspheres of example 1 of the present application after 5d aging;
FIG. 6 is a graph showing the initial particle size distribution of the polymer microspheres of example 1 of the present application after 9d aging;
FIG. 7 is an initial optical micrograph of polymeric microspheres of example 1 of the present application;
FIG. 8 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 5 hours;
FIG. 9 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 1 d;
FIG. 10 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 3 days;
FIG. 11 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 5 days;
FIG. 12 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 7 d;
FIG. 13 is an optical micrograph of the polymer microsphere of example 1 of the present application after aging for 9 d;
FIG. 14 is a schematic diagram showing the synthesis process and the controlled release process of the polymer microsphere according to the embodiment of the present application;
FIG. 15 is a graph showing the pressure of plugging with the polymer microspheres of example 1 according to the present application as a function of the PV number of water injections;
FIG. 16 is a plot of pressure versus the number of water injections PV for single sand pipe displacement using the polymer microspheres of example 1 of the present application;
FIG. 17 is a plot of percent oil-water as a function of water injection PV number for single sand pipe displacement using the polymer microspheres of example 1 of the present application;
FIG. 18 is a plot of recovery ratio as a function of water injection PV number for single sand pipe displacement using the polymer microspheres of example 1 of the present application;
FIG. 19 is a graph showing the initial particle size distribution of polymer microspheres of example 2 of the present application;
FIG. 20 is a graph showing the initial particle size distribution of the polymer microspheres of example 2 of the present application after aging for 1 d;
FIG. 21 is a graph showing the initial particle size distribution of the polymer microspheres of example 2 of the present application after 3d aging;
FIG. 22 is a graph showing the initial particle size distribution of the polymer microspheres of example 2 of the present application after 6d aging;
FIG. 23 is an initial optical micrograph of polymer microspheres of example 2 of the present application;
FIG. 24 is an optical micrograph of the polymer microsphere of example 2 of the present application after 5 hours of aging;
FIG. 25 is an optical micrograph of the polymer microsphere of example 2 of the present application after aging for 1 d;
FIG. 26 is an optical micrograph of the polymer microsphere of example 2 of the present application after aging for 3 d;
FIG. 27 is an optical micrograph of the polymer microsphere of example 2 of the present application after aging for 6 d;
FIG. 28 is a graph showing the initial particle size distribution of polymer microspheres of example 3 of the present application;
FIG. 29 is a graph showing the initial particle size distribution of the polymer microspheres of example 3 of the present application after aging for 1 d;
FIG. 30 is a graph showing the initial particle size distribution of the polymer microspheres of example 3 of the present application after 3d aging;
FIG. 31 is a graph showing the initial particle size distribution of the polymer microspheres of example 3 of the present application after 6d aging;
FIG. 32 is an initial optical micrograph of polymer microspheres of example 3 of the present application;
FIG. 33 is an optical micrograph of the polymer microsphere of example 3 of the present application after aging for 5 hours;
FIG. 34 is an optical micrograph of the polymer microsphere of example 3 of the present application after aging for 1 d;
FIG. 35 is an optical micrograph of the polymer microsphere of example 3 of the present application after aging for 3 d;
FIG. 36 is an optical micrograph of polymer microspheres of example 3 of the present application after 6d aging.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail hereinafter with reference to the accompanying drawings. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be arbitrarily combined with each other.
In the present application, "the total mass of the entire system for preparing the polymer microspheres" refers to the total mass of all raw materials and reagents added to prepare the polymer microspheres before the reaction.
In the present application, when a mass fraction of a certain raw material or agent is referred to as the mass of the effective ingredient in the raw material or agent, the mass fraction is the mass of the entire system for preparing the polymer microsphere.
The embodiment of the application provides a preparation method of polymer microspheres capable of being subjected to secondary crosslinking, which comprises the following steps:
emulsifying gelatin in oil phase;
adding metal salt into emulsified gelatin and solidifying the gelatin, so that the metal salt is coated inside the solidified gelatin to obtain the core of the polymer microsphere;
and coating a polymer shell on the outer part of the core by adopting an inverse emulsion polymerization method to obtain the polymer microsphere.
In an embodiment of the present application, the method for preparing the secondary cross-linkable polymer microsphere may include:
(1) Preparing the oil phase using an oil and a surfactant;
(2) Adding an aqueous solution of gelatin into the oil phase obtained in the step (1), and emulsifying the gelatin in the oil phase;
(3) Dropwise adding metal salt into the system obtained in the step (2), cooling to solidify the gelatin, and coating the metal salt in the solidified gelatin to obtain the core of the polymer microsphere;
(4) Mixing a monomer forming the polymer shell, a cross-linking agent and an oxidation initiator to form a mixed solution containing the monomer, adding the mixed solution containing the monomer into the system obtained in the step (3), and coating the mixed solution containing the monomer on the outer side of the core of the polymer microsphere;
(5) Adding a reduced initiator into the system obtained in the step (4), and performing inverse emulsion polymerization reaction on the reduced initiator and the monomer-containing mixed solution coated on the outer side of the core of the polymer microsphere, so that a polymer shell is coated on the outer side of the core of the polymer microsphere, thereby obtaining the polymer microsphere.
In an embodiment of the present application, in the step (3), the metal salt may be an organic acid salt of a metal selected from any one of chromium, zirconium and aluminum, and the organic acid may be selected from any one of acetic acid, citric acid and lactic acid.
In an embodiment of the present application, the metal salt may be selected from any one of chromium acetate, zirconium acetate, aluminum citrate, zirconium citrate, and chromium lactate.
In embodiments of the present application, the metal salt may comprise from 1.91% to 2.84% by mass of the total mass of the entire system in which the polymeric microspheres are prepared.
In embodiments of the application, the temperature may be reduced to below 10 ℃ and stirring continued until the gelatin solidifies.
Optionally, the duration of the continuous stirring may be 15 minutes to 40 minutes, for example, may be 20 minutes.
In an embodiment of the present application, step (1) may include: mixing the oil and the surfactant, stirring and heating to a first temperature to obtain the oil phase.
In an embodiment of the present application, the oil may be selected from any one or more of white oil and paraffinic oil.
In embodiments of the present application, the surfactant may be selected from any one or more of Span80, OP-4, and Span-60.
In an embodiment of the present application, the first temperature may be 45 ℃ to 68 ℃, for example, 55 ℃ to 60 ℃.
In embodiments of the application, the oil may comprise 38.4% to 40.71% by mass of the total mass of the system in which the polymeric microspheres are prepared, for example, may comprise 38.55%.
In embodiments of the application, the surfactant may comprise from 5.55% to 7.86% by mass of the total mass of the system in which the polymeric microspheres are prepared, for example, may comprise 7.71%.
In an embodiment of the present application, step (2) may include:
(2-1) adding an aqueous solution of gelatin to the oil phase obtained in step (1) and emulsifying the gelatin under stirring at a second temperature;
(2-2) cooling the system obtained in the step (2-1) and reducing the stirring speed, and continuing emulsifying the gelatin under the third temperature and stirring condition.
In an embodiment of the present application, in step (2-1), the second temperature may be 45 ℃ to 68 ℃, for example, may be 55 ℃ to 60 ℃; the speed of agitation may be 800 rpm to 1200 rpm, for example, 800 rpm to 1000 rpm; the gelatin emulsifying time may be 15 minutes to 40 minutes, for example, 15 minutes to 20 minutes.
In embodiments of the application, the gelatin may comprise 1% to 3% of the total mass of the entire system in which the polymeric microspheres are prepared.
In an embodiment of the present application, in step (2-2), the third temperature may be 30 ℃ to 45 ℃, for example, may be 40 ℃ to 45 ℃; the stirring speed may be reduced to 500 to 800 rpm, for example, 500 to 600 rpm; the time for continuing emulsification of gelatin may be 1 hour or more.
In an embodiment of the present application, step (4) may include:
(4-1) mixing acrylic acid, acrylamide, a crosslinking agent, an oxidation initiator and water and adjusting the pH with a base to obtain the monomer-containing mixed solution;
(4-2) dropwise adding the monomer-containing mixed solution into the system obtained in the step (3), continuously stirring and introducing nitrogen gas, so that the monomer-containing mixed solution is coated on the outer side of the core of the polymer microsphere.
In an embodiment of the present application, in step (4-1), the crosslinking agent may be selected from any one or both of N, N-methylenebisacrylamide and divinylbenzene; the oxidation initiator can be selected from any one or two of potassium persulfate and ammonium persulfate; the base can be selected from any one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine; the pH can be adjusted to 5 to 8 with a base.
In an embodiment of the present application, in step (4-1), the mass of the acrylic acid may be 1.45% to 2.90% of the total mass of the entire system for preparing the polymer microsphere, for example, may be 1.93%; the mass of the acrylamide may be 16.38% to 17.83% of the total mass of the entire system in which the polymer microsphere is prepared, for example, may be 17.35%; the mass of the crosslinking agent may be less than 2% of the total mass of the entire system in which the polymer microsphere is prepared, for example, may be 0.02%; the mass of the oxidized initiator may be 0.025% to 1% of the total mass of the entire system in which the polymer microsphere is prepared, for example, may be 0.1%.
In an embodiment of the present application, in the step (4-2), the speed of the continuous stirring may be 500 rpm to 800 rpm, for example, 700 rpm to 800 rpm.
In the embodiment of the application, in the step (4-2), the flow rate of the nitrogen gas may be 0.01m 3/h to 0.05m 3/h, the flow time may be more than 30 minutes, and the purity may be 99.5% to 99.999%.
In an embodiment of the present application, step (5) may include: and (3) adding the reduced initiator into the system obtained in the step (4), and controlling the temperature of the system at a fourth temperature to perform inverse emulsion polymerization reaction, so that the core of the polymer microsphere is coated with a polymer shell, thereby obtaining the polymer microsphere.
In embodiments of the application, the fourth temperature may not exceed 60 ℃; the reaction time of the inverse emulsion polymerization may be 1 hour to 2.5 hours, for example, may be 1 hour.
In an embodiment of the present application, the reduced initiator may be selected from any one or more of an aqueous sodium bisulfite solution, an aqueous sodium sulfite solution, an aqueous ferrous sulfate solution, and N-N dimethylaniline.
In embodiments of the application, the mass (in terms of active ingredient) of the reduced initiator may be 0.025% to 1% of the total mass of the entire system in which the polymeric microspheres are prepared, e.g., may be 0.04%; the mass fraction of the sodium bisulphite aqueous solution may be 0.05% to 1%.
In an embodiment of the present application, the total mass of the entire system for preparing the polymer microspheres is made up to 100% with water, which includes a first portion of water for preparing an aqueous solution of gelatin, a second portion of water for preparing a mixed solution containing a monomer in step (4-1), and when the reduced initiator in step (5) is an aqueous solution of an inorganic salt, water further includes a third portion of water for preparing an aqueous solution of the reduced initiator.
In an embodiment of the present application, the method for preparing the secondary cross-linkable polymer microsphere may include:
(1) Mixing the oil and the surfactant, stirring and heating to a first temperature to obtain the oil phase;
(2-1) adding an aqueous solution of gelatin to the oil phase obtained in step (1) and emulsifying the gelatin under stirring at a second temperature;
(2-2) cooling the system obtained in the step (2-1) and reducing the stirring speed, and continuing emulsifying the gelatin under the third temperature and stirring condition;
(3) Dropwise adding metal salt into the system obtained in the step (2), cooling to solidify the gelatin, and coating the metal salt in the solidified gelatin to obtain the core of the polymer microsphere;
(4-1) mixing acrylic acid, acrylamide, a crosslinking agent, an oxidation initiator and water and adjusting the pH with a base to obtain the monomer-containing mixed solution;
(4-2) dropwise adding the monomer-containing mixed solution into the system obtained in the step (3), continuously stirring and introducing nitrogen gas, so that the monomer-containing mixed solution is coated on the outer part of the core of the polymer microsphere;
(5) And (3) adding the aqueous solution of the reduced initiator into the system obtained in the step (4), and controlling the temperature of the system at a fourth temperature to perform inverse emulsion polymerization reaction, so that the outer part of the core of the polymer microsphere is coated with a polymer shell, thereby obtaining the polymer microsphere.
The embodiment of the application also provides a polymer microsphere capable of being subjected to secondary crosslinking, which comprises a core and a shell coated outside the core, wherein the core comprises metal salt and gelatin coated outside the metal salt, and the shell is a polymer with a three-dimensional network structure.
In an embodiment of the present application, the metal salt may be an organic acid salt of a metal selected from any one of chromium, zirconium and aluminum, and the organic acid may be selected from any one of acetic acid, citric acid and lactic acid.
In an embodiment of the present application, the metal salt may be selected from any one of chromium acetate, zirconium acetate, aluminum citrate, zirconium citrate, and chromium lactate.
In embodiments of the present application, the housing may be a polymer formed from acrylic acid monomers, sodium acrylate monomers, and acrylamide monomers.
In an embodiment of the present application, the polymer microsphere may be obtained by the preparation method of the polymer microsphere capable of being secondarily crosslinked as described above.
In embodiments of the application, the average particle size of the polymeric microspheres may be 5 μm or less, for example, 0.4658 μm, 0.7558 μm, 1.0258 μm.
In an embodiment of the application, the shell may house a plurality of cores, and one core may house a plurality of metal salt molecules.
The embodiment of the application also provides the application of the polymer microsphere capable of being subjected to secondary crosslinking in oilfield exploitation as a plugging agent or an oil displacement agent.
The raw materials and reagents used in the following examples were all commercially available products unless otherwise specified.
Example 1
(1) 38.55G of oil (white oil) and 7.71g of surfactant (Span 80) were weighed into a three-necked flask, heated to 55 ℃ with stirring, and an oil phase was formed;
(2-1) weighing 1.16g of gelatin dry powder and 8.84g of water to prepare an aqueous solution of gelatin, adding the aqueous solution into a three-neck flask, rapidly stirring at a stirring speed of 900 revolutions per minute, simultaneously keeping the temperature of the three-neck flask at 55 ℃, and emulsifying for 20 minutes;
(2-2) lowering the temperature of the system in the three-neck flask to 40 ℃, simultaneously lowering the stirring speed to 500 rpm, then continuously stirring, keeping the system constant at 40 ℃, and keeping the constant temperature for reaction for 1.5 hours to enable the gelatin to be continuously emulsified;
(3) Adding 2.31g of chromium acetate solution into a three-neck flask by adopting a dropwise adding mode, reducing the system temperature to 5 ℃ by adopting an ice water bath, and continuously stirring for 20 minutes to solidify gelatin, so that chromium acetate is coated in the solidified gelatin to obtain the core of the polymer microsphere;
(4-1) mixing 1.93g of acrylic acid, 17.35g of acrylamide, 0.02g of a crosslinking agent (N, N-methylenebisacrylamide), 0.1g of an oxidation initiator (ammonium persulfate) and 17.96g of water and adjusting the pH to about 7.5 with 1.07g of sodium hydroxide to obtain the monomer-containing mixed solution;
(4-2) adding the monomer-containing mixed solution prepared in the step (4-1) into the system obtained in the step (3) in a dropwise manner, properly increasing the stirring speed to 750 rpm, and introducing high-purity nitrogen (with the purity of 99.999%) at the flow rate of 0.02m 3/h for 50 minutes to coat the monomer-containing mixed solution on the outer side of the core of the polymer microsphere;
(5) Adding 0.04g of sodium bisulphite into 2.96g of water to prepare a reduced initiator, adding the reduced initiator into the system obtained in the step (4), spontaneously raising the temperature of the system from 20 ℃, adopting a cold water bath to control the temperature to be not more than 60 ℃, keeping the temperature for continuous reaction for 1 hour, and then cooling to room temperature to obtain the polymer microsphere.
Example 2
(1) 40.71G of oil (white oil) and 5.55g of surfactant (Span 80) are weighed into a three-neck flask, stirred and heated to 60 ℃ to form an oil phase;
(2-1) weighing 1.74g of gelatin dry powder and 8.26g of water to prepare an aqueous solution of gelatin, adding the aqueous solution into a three-neck flask, rapidly stirring at a stirring speed of 800 revolutions per minute, simultaneously maintaining the temperature of the three-neck flask at 60 ℃, and emulsifying for 15 minutes;
(2-2) lowering the temperature of the system in the three-neck flask to 40 ℃, simultaneously lowering the stirring speed to 500rpm, then continuously stirring, keeping the system constant at 40 ℃, and keeping the constant temperature for 2 hours for reaction, so that the gelatin is continuously emulsified;
(3) Adding 1.91g of aluminum citrate solution into a three-neck flask by adopting a dropwise adding mode, reducing the system temperature to 10 ℃ by adopting an ice water bath, continuously stirring for 15 minutes, solidifying gelatin, and further coating aluminum citrate in the solidified gelatin to obtain the core of the polymer microsphere;
(4-1) mixing 1.93g of acrylic acid, 17.35g of acrylamide, 0.05g of a crosslinking agent (N, N-methylenebisacrylamide), 0.05g of an oxidation initiator (potassium persulfate) and 18.38g of water and adjusting the pH to about 7.5 with 1.07g of sodium hydroxide to obtain the monomer-containing mixed solution;
(4-2) adding the monomer-containing mixed solution prepared in the step (4-1) into the system obtained in the step (3) in a dropwise manner, properly increasing the stirring speed to 700 revolutions per minute, and introducing high-purity nitrogen (with the purity of 99.999%) at the flow rate of 0.02m 3/h for 30 minutes to coat the monomer-containing mixed solution on the outer side of the core of the polymer microsphere;
(5) Adding 0.04g of sodium bisulphite into 2.96g of water to prepare a reduced initiator, adding the reduced initiator into the system obtained in the step (4), spontaneously raising the temperature of the system from 20 ℃, adopting a cold water bath to control the temperature to be not more than 60 ℃, keeping the temperature for continuous reaction for 1 hour, and then cooling to room temperature to obtain the polymer microsphere.
Example 3
(1) 38.40G of oil (white oil) and 7.86g of surfactant (Span 80) were weighed into a three-necked flask, heated to 57 ℃ with stirring, and an oil phase was formed;
(2-1) weighing 2.32g of gelatin dry powder and 7.68g of water to prepare an aqueous solution of gelatin, adding the aqueous solution into a three-neck flask, rapidly stirring at a stirring speed of 1000 revolutions per minute, keeping the temperature of the three-neck flask at 57 ℃, and emulsifying for 20 minutes;
(2-2) reducing the temperature of the system in the three-neck flask to 42 ℃, simultaneously reducing the stirring speed to 600 revolutions per minute, then continuously stirring, keeping the system constant at 42 ℃, and reacting for 1.7 hours at constant temperature to continuously emulsify gelatin;
(3) Adding 2.84 zirconium acetate solution into a three-neck flask in a dropwise adding mode, reducing the system temperature to 0 ℃ by adopting an ice water bath, and continuously stirring for 15 minutes to solidify gelatin, so that zirconium acetate is coated in the solidified gelatin to obtain the core of the polymer microsphere;
(4-1) mixing 1.93g of acrylic acid, 17.35g of acrylamide, 0.02g of a crosslinking agent (N, N-methylenebisacrylamide), 0.1g of an oxidation initiator (ammonium persulfate) and 17.43g of water and adjusting the pH to about 7.5 with 1.07g of sodium hydroxide to obtain the monomer-containing mixed solution;
(4-2) adding the monomer-containing mixed solution prepared in the step (4-1) into the system obtained in the step (3) in a dropwise manner, properly increasing the stirring speed to 800 revolutions per minute, and introducing high-purity nitrogen (with the purity of 99.999%) at the flow rate of 0.02m 3/h for 40 minutes to coat the monomer-containing mixed solution on the outer side of the core of the polymer microsphere;
(5) Adding 0.04g of sodium bisulphite into 2.96g of water to prepare a reduced initiator, adding the reduced initiator into the system obtained in the step (4), spontaneously raising the temperature of the system from 20 ℃, adopting a cold water bath to control the temperature to be not more than 60 ℃, keeping the temperature for continuous reaction for 1 hour, and then cooling to room temperature to obtain the polymer microsphere.
Test example 1-1
The polymer microspheres prepared in example 1 were formulated into an aqueous dispersion having a concentration of 5000mg/L, and then aged at 65℃and then tested for average particle size and particle size distribution after various aging times using a Markov laser particle sizer MS3000 instrument, as shown in Table 1 and FIGS. 1 to 6.
TABLE 1
| Aging time | Average particle diameter (μm) |
| 0d | 0.4658 |
| 1d | 0.7353 |
| 3d | 1.3432 |
| 5d | 8.5361 |
| 7d | 121.6347 |
| 9d | 127.7035 |
FIGS. 1 to 6 are graphs showing particle size distribution of the polymer microspheres prepared in example 1 at various aging times.
The polymer microspheres prepared in example 1 are swelled at 65 ℃, and the particle size of the polymer microspheres is unimodal when the polymer microspheres are swelled, and the average particle size is 0.4658 mu m; along with the extension of the aging time, the particle size distribution starts to be in a bimodal form but is not obvious when the aging time is 5d, and along with the further extension of the aging time, the large particle size peak moves to the high particle size direction, which indicates that the chromium acetate in the core of the polymer microsphere is gradually released, and the chromium acetate can be used as a secondary crosslinking agent to cause secondary crosslinking between the polymer microspheres to form a large secondary crosslinking body; as the aging time continues to increase, the chromium acetate in the polymer microspheres is completely released, and the average particle size of the polymer microspheres can reach 127.7035 mu m.
Test examples 1 to 2
In order to more clearly observe the release of chromium acetate from the polymer microspheres, the swelling state of the polymer microsphere aqueous dispersion with the polymer microsphere concentration of 5000mg/L at 65 ℃ for different aging times was observed by an optical microscope. Fig. 7 to 13 are optical microscopic images of the polymer microspheres prepared in example 1 at various aging times.
It can be seen that the distribution state of the polymer microspheres is more dispersed when swelling is started; along with the extension of aging time, secondary crosslinking is generated between the microspheres due to the release of the secondary crosslinking agent, so that larger agglomerates are formed; over 7d aging, secondary crosslinked agglomerated particles of tens of microns to nearly hundreds of microns were observed.
The experimental result and the previous particle size measurement experimental result are combined to find that the initial particle size of the polymer microsphere is small, so that the polymer microsphere can go deep into the oil reservoir; the polymer microsphere is swelled when aged at a certain temperature, so that the polymer microsphere is swelled under the action of the temperature and mineralization degree of formation water, the pore diameter of the three-dimensional network structure of the shell is enlarged, chromium acetate in the nucleus is released, the released chromium acetate can be hydrolyzed to form polynuclear hydroxyl bridging ions, and the polynuclear hydroxyl bridging ions are secondarily crosslinked with the hydrolyzed polymer microsphere containing carboxyl to form a large secondary crosslinking body, so that the polymer microsphere prepared by the embodiment of the application has better plugging capacity and oil displacement capacity and can be used as a plugging agent or an oil displacement agent in oil field exploitation. FIG. 14 is a schematic diagram showing the synthesis process and the controlled release process of the polymer microsphere according to the embodiment of the present application.
Test examples 1 to 3
Single sand pipe plugging performance test of polymer microspheres of the embodiment of the application
Adopting artificial dry filling, wherein the average permeability of the sand pipe is about 2.26 Dc; the experimental strata simulate the total water mineralization degree: 5863.27mg/L; the polymer microspheres prepared in example 1 were formulated as an aqueous dispersion with a concentration of 5000mg/L, and then injected into the slugs: 1PV, after 7d of constant temperature waiting and condensing at 65 ℃, water injection displacement is carried out, and the displacement speed is that: 0.3mL/min.
The blocking effect of the polymer microspheres prepared in example 1 is shown in table 2 and fig. 15; FIG. 15 is a graph showing the pressure change with the PV number of injected water in plugging experiments for the polymer microspheres of example 1 of the present application.
TABLE 2
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As can be seen from the single sand pipe plugging experimental results, the plugging rate of the polymer microsphere aqueous dispersion liquid in the embodiment of the application can reach 97.5%, and the average residual resistance coefficient of the sand pipe can be seen, the residual resistance coefficient of 39.48 can be obtained by injecting the polymer microsphere in the embodiment of the application, and the plugging effect is quite obvious. In addition, the inlet pressure of the sand pipe shows more obvious up-and-down fluctuation, the subsequent secondary plugging can be generated after the primary plugging pressure breaks through, the overall pressure shows a gradual rising trend, and the formed secondary cross-linked aggregate is larger and the plugging strength is better.
Test examples 1 to 4
Single sand pipe simulated oil displacement experiment of polymer microspheres of the embodiment of the application
Adopting manual dry filling, and the average permeability of the sand pipe is about 2.26 Dc; the experimental strata simulate the total water mineralization degree: 5863.27mg/L; the polymer microspheres prepared in example 1 were formulated as an aqueous dispersion with a concentration of 5000mg/L, then aged for 7d in a thermostatted oven at 65 ℃ and then slugged: 0.2PV; experimental simulation crude oil viscosity (relatively low viscosity): about 10mPa s (65 ℃) and crude oil is prepared by adding coal oil; displacement speed: 0.3mL/min. The displacement results of the single sand pipe simulated flooding experiment are shown in table 3 and fig. 16 to 18.
TABLE 3 Table 3
FIG. 15 is a plot of pressure versus the number of water injections PV for single sand pipe displacement using the polymer microspheres of example 1 of the present application; FIG. 16 is a plot of percent oil-water as a function of water injection PV number for single sand pipe displacement using the polymer microspheres of example 1 of the present application; FIG. 17 is a plot of recovery ratio as a function of water injection PV number for single sand pipe displacement using the polymer microspheres of example 1 of the present application.
It can be seen that the pressure fluctuation at the inlet end of the polymer microsphere injected with the embodiment of the application is quite obvious, because the polymer microsphere undergoes a secondary crosslinking reaction after aging at high temperature (65 ℃), larger aggregates are formed between the microspheres, the particle size is larger than that of the cementing body formed by the original core-shell microsphere, the strength is stronger, the polymer microsphere is slowly moved forward under the pushing of the subsequent water injection pressure, and the pressure fluctuation change of plugging-breaking-re-plugging is formed.
Test example 2-1
The polymer microspheres prepared in example 2 were formulated into an aqueous dispersion having a concentration of 5000mg/L, then aged at 65℃and then tested for average particle size and particle size distribution after various aging times using a Markov laser particle sizer MS3000 instrument, as shown in Table 4 and FIGS. 19 to 22.
TABLE 4 Table 4
| Aging time | Average particle diameter (μm) |
| 0d | 0.7558 |
| 1d | 1.0977 |
| 3d | 1.2315 |
| 6d | 87.0610 |
Fig. 19 to 22 are particle size distribution diagrams of the polymer microspheres prepared in example 2 at various aging times. It can be seen that the particle size of the polymer microspheres is unimodal at the beginning of swelling, and the average particle size is 0.7558 μm; with the extension of aging time, the secondary crosslinking agent aluminum citrate is completely released, and the average particle size of the polymer microsphere can reach 87.0610 mu m.
Test example 2-2
In order to more clearly observe the release of aluminum citrate in the polymer microspheres, the swelling states of the polymer microsphere aqueous dispersion with the polymer microsphere concentration of 5000mg/L at 65 ℃ and different aging times are observed by an optical microscope. FIGS. 23 to 27 are optical microscopic images of the polymer microspheres prepared in example 2 at various aging times.
It can be seen that the distribution state of the polymer microspheres is more dispersed when swelling is started; along with the extension of aging time, secondary crosslinking is generated between the microspheres due to the release of the secondary crosslinking agent, so that larger agglomerates are formed; over 6d aging, secondary crosslinked agglomerated particles of tens of microns to nearly hundreds of microns can be observed.
The experimental result and the previous particle size measurement experimental result are combined to find that the initial particle size of the polymer microsphere is small and the polymer microsphere can go deep into the oil reservoir; under the action of the temperature and mineralization of formation water, the secondary crosslinking agent aluminum citrate is released along with the expansion of the microspheres, and the released secondary crosslinking agent is hydrolyzed to form polynuclear hydroxyl bridging ions, and the polynuclear hydroxyl bridging ions are secondarily crosslinked with the hydrolyzed carboxyl-containing polymer microspheres to form large secondary crosslinking bodies, so that the polymer microspheres prepared by the embodiment of the application have better plugging capacity and oil displacement capacity and can be used as plugging agents or oil displacement agents in oilfield exploitation.
Test example 3-1
The polymer microspheres prepared in example 3 were formulated into an aqueous dispersion having a concentration of 5000mg/L, then aged at 65℃and then tested for average particle size and particle size distribution after various aging times using a Markov laser particle sizer MS3000 instrument, as shown in Table 5 and FIGS. 28 to 31.
TABLE 5
| Aging time | Average particle diameter (μm) |
| 0d | 1.0258 |
| 1d | 1.9484 |
| 3d | 3.5374 |
| 6d | 206.1791 |
FIGS. 28 to 31 are graphs showing particle size distribution of the polymer microspheres prepared in example 3 at various aging times. It can be seen that the particle size of the polymer microspheres is unimodal when the polymer microspheres are initially swelled, and the average particle size is 1.0258 mu m; along with the extension of aging time, the zirconium acetate serving as a secondary crosslinking agent is completely released, and the average particle size of the polymer microsphere can reach 206.1791 mu m.
Test example 3-2
In order to more clearly observe the release of zirconium acetate in the polymer microspheres, the swelling state of the polymer microsphere aqueous dispersion with the polymer microsphere concentration of 5000mg/L at 65 ℃ for different aging times was observed by an optical microscope. FIGS. 32 to 36 are optical microscopic images of the polymer microspheres prepared in example 3 at various aging times.
It can be seen that the distribution state of the polymer microspheres is more dispersed when swelling is started; along with the extension of aging time, the microspheres are subjected to secondary crosslinking due to the release of a secondary crosslinking agent zirconium acetate, so that larger agglomerates are formed; over 6d aging, secondary crosslinked agglomerated particles of several hundred microns were observed.
The experimental result and the previous particle size measurement experimental result are combined to find that the initial particle size of the polymer microsphere is small and the polymer microsphere can go deep into the oil reservoir; under the action of the temperature and mineralization of formation water, the zirconium acetate serving as a secondary crosslinking agent is released along with the expansion of the microspheres, and the released secondary crosslinking agent is hydrolyzed to form polynuclear hydroxyl bridging ions, and the polynuclear hydroxyl bridging ions and the hydrolyzed carboxyl-containing polymer microspheres are subjected to secondary crosslinking to form large secondary crosslinking bodies, so that the polymer microspheres prepared by the embodiment of the application have better plugging capacity and oil displacement capacity and can be used as plugging agents or oil displacement agents in oilfield exploitation.
Although the embodiments of the present application are described above, the embodiments are only used for facilitating understanding of the present application, and are not intended to limit the present application. Any person skilled in the art can make any modification and variation in form and detail without departing from the spirit and scope of the present disclosure, but the scope of the present disclosure is to be determined by the appended claims.
Claims (18)
1. A method for preparing a polymer microsphere capable of being subjected to secondary crosslinking, comprising the steps of:
(1) Mixing oil and a surfactant, stirring and heating to a first temperature to obtain an oil phase;
(2-1) adding an aqueous solution of gelatin to the oil phase obtained in step (1) and emulsifying the gelatin under stirring at a second temperature;
(2-2) cooling the system obtained in the step (2-1) and reducing the stirring speed, and continuing emulsifying the gelatin under the third temperature and stirring condition;
(3) Dropwise adding metal salt into the system obtained in the step (2), cooling to solidify the gelatin, and coating the metal salt in the solidified gelatin to obtain the core of the polymer microsphere;
(4-1) mixing acrylic acid, acrylamide, a cross-linking agent, an oxidation initiator and water and adjusting the pH with alkali to obtain a mixed solution containing monomers;
(4-2) dropwise adding the monomer-containing mixed solution into the system obtained in the step (3), continuously stirring and introducing nitrogen gas, so that the monomer-containing mixed solution is coated on the outer part of the core of the polymer microsphere;
(5) Adding a reduced initiator into the system obtained in the step (4), controlling the temperature of the system at a fourth temperature, and performing inverse emulsion polymerization reaction on the reduced initiator and the monomer-containing mixed solution coated on the outer side of the core of the polymer microsphere so as to coat a polymer shell on the outer side of the core of the polymer microsphere, thereby obtaining the polymer microsphere;
wherein in step (3), the metal salt is an organic acid salt of a metal selected from any one of chromium, zirconium and aluminum, and the organic acid is selected from any one of acetic acid, citric acid and lactic acid;
In step (4-1), the crosslinking agent is selected from any one or two of N, N-methylenebisacrylamide and divinylbenzene; the oxidation initiator is selected from any one or two of potassium persulfate and ammonium persulfate; the alkali is selected from any one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine; adjusting the pH to 5 to 8 with a base;
The reduction initiator is selected from any one or more of sodium bisulphite aqueous solution, sodium sulfite aqueous solution, ferrous sulfate aqueous solution and N-N dimethylaniline.
2. The production method according to claim 1, wherein in the step (3), the metal salt is selected from any one of chromium acetate, zirconium acetate, aluminum citrate, zirconium citrate and chromium lactate.
3. The production method according to claim 1, wherein the mass of the metal salt is 1.91% to 2.84% of the total mass of the whole system in which the polymer microsphere is produced.
4. The preparation method according to claim 1, wherein in step (3), the temperature is lowered to 10 ℃ or lower and stirring is continued until the gelatin is solidified.
5. The production method according to claim 4, wherein in the step (3), the duration of stirring is 15 minutes to 40 minutes.
6. The production method according to claim 1 or 2, wherein the oil is selected from any one or more of white oil and paraffinic oil.
7. The production method according to claim 1 or 2, wherein the surfactant is selected from any one or more of Span80, OP-4, and Span-60.
8. The method of manufacture of claim 1, wherein the first temperature is 45 ℃ to 68 ℃.
9. The production method according to claim 1 or 2, wherein in the step (2-1), the second temperature is 45 ℃ to 68 ℃, the stirring speed is 800 rpm to 1200 rpm, and the time for emulsification of gelatin is 15 minutes to 40 minutes.
10. The production method according to claim 1 or 2, wherein in step (2-1), the mass of the gelatin accounts for 1% to 3% of the total mass of the whole system in which the polymer microspheres are produced.
11. The production method according to claim 1 or 2, wherein in the step (2-2), the third temperature is 30 ℃ to 45 ℃, the stirring speed is reduced to 500 rpm to 800 rpm, and the time for continuing emulsification of gelatin is 1 hour or more.
12. The production method according to claim 1 or 2, wherein in step (4-1), the mass of the acrylic acid is 1.45% to 2.9% of the total mass of the whole system in which the polymer microsphere is produced; the mass of the acrylamide accounts for 16.38 to 17.83 percent of the total mass of the whole system for preparing the polymer microsphere; the mass of the cross-linking agent accounts for less than 2% of the total mass of the whole system for preparing the polymer microsphere; the mass of the oxidized initiator is 0.025% to 1% of the total mass of the entire system in which the polymeric microspheres are prepared.
13. The production method according to claim 1 or 2, wherein in step (4-2), the speed of continuous stirring is 500 rpm to 800 rpm.
14. The production method according to claim 1 or 2, wherein the fourth temperature is not more than 60 ℃; the inverse emulsion polymerization reaction time is 1 hour to 2.5 hours.
15. The production method according to claim 1 or 2, wherein the mass of the reduced initiator is 0.025% to 1% of the total mass of the whole system in which the polymer microsphere is produced.
16. A polymer microsphere capable of being subjected to secondary crosslinking is characterized in that,
Obtained by the production method according to any one of claims 1 to 15.
17. The polymeric microspheres of claim 16 wherein the polymeric microspheres have an average particle size of 5 μm or less.
18. Use of the polymeric microspheres according to claim 16 or 17 as a plugging or flooding agent in oilfield exploitation.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503617A (en) * | 2009-03-05 | 2009-08-12 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated phase change energy storage material and preparation thereof |
| KR20170064917A (en) * | 2015-12-02 | 2017-06-12 | 주식회사 나노브릭 | Emulsion, Gelly Balls, and Spheres Containing Color Nanocomposite |
| CN108816162A (en) * | 2018-05-22 | 2018-11-16 | 安徽大学 | Preparation method of inorganic polymer hybrid microspheres with Yolk-Shell structure |
| CN109134768A (en) * | 2018-08-28 | 2019-01-04 | 黑龙江吉地油田服务股份有限公司 | A kind of nano grade polymer microballoon and preparation method thereof |
| CN109666099A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Core-shell polymers microballoon and preparation method thereof |
| CN111423864A (en) * | 2020-05-12 | 2020-07-17 | 燕山大学 | Cementing profile control agent for fractured reservoir and application and use method thereof |
| CN111729625A (en) * | 2020-06-15 | 2020-10-02 | 宁波锋成先进能源材料研究院 | Nano composite micro-rubber ball and preparation method and application thereof |
| CN112169719A (en) * | 2020-09-23 | 2021-01-05 | 中国石油大学(北京) | AM/PF microsphere with multiple cross-linked structure and preparation method and application thereof |
-
2021
- 2021-08-10 CN CN202110914215.4A patent/CN113634204B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503617A (en) * | 2009-03-05 | 2009-08-12 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated phase change energy storage material and preparation thereof |
| KR20170064917A (en) * | 2015-12-02 | 2017-06-12 | 주식회사 나노브릭 | Emulsion, Gelly Balls, and Spheres Containing Color Nanocomposite |
| CN109666099A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Core-shell polymers microballoon and preparation method thereof |
| CN108816162A (en) * | 2018-05-22 | 2018-11-16 | 安徽大学 | Preparation method of inorganic polymer hybrid microspheres with Yolk-Shell structure |
| CN109134768A (en) * | 2018-08-28 | 2019-01-04 | 黑龙江吉地油田服务股份有限公司 | A kind of nano grade polymer microballoon and preparation method thereof |
| CN111423864A (en) * | 2020-05-12 | 2020-07-17 | 燕山大学 | Cementing profile control agent for fractured reservoir and application and use method thereof |
| CN111729625A (en) * | 2020-06-15 | 2020-10-02 | 宁波锋成先进能源材料研究院 | Nano composite micro-rubber ball and preparation method and application thereof |
| CN112169719A (en) * | 2020-09-23 | 2021-01-05 | 中国石油大学(北京) | AM/PF microsphere with multiple cross-linked structure and preparation method and application thereof |
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