CN107286920B - Microspheric double-comb block polymer profile control and flooding agent and preparation method thereof - Google Patents
Microspheric double-comb block polymer profile control and flooding agent and preparation method thereof Download PDFInfo
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- CN107286920B CN107286920B CN201610227506.5A CN201610227506A CN107286920B CN 107286920 B CN107286920 B CN 107286920B CN 201610227506 A CN201610227506 A CN 201610227506A CN 107286920 B CN107286920 B CN 107286920B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 239000004005 microsphere Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 37
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 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 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 18
- 229920001400 block copolymer Polymers 0.000 claims description 17
- 239000000443 aerosol Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 amine compound Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 3
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 claims description 3
- IOHJQSFEAYDZGF-UHFFFAOYSA-N 2-dodecyloxirane Chemical compound CCCCCCCCCCCCC1CO1 IOHJQSFEAYDZGF-UHFFFAOYSA-N 0.000 claims description 3
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 3
- QJFMXJDSWJZAAL-UHFFFAOYSA-N n,n,n',n'-tetrakis(prop-2-enyl)ethane-1,2-diamine Chemical compound C=CCN(CC=C)CCN(CC=C)CC=C QJFMXJDSWJZAAL-UHFFFAOYSA-N 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 229940099427 potassium bisulfite Drugs 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 claims description 2
- CURJNMSGPBXOGK-UHFFFAOYSA-N n',n'-di(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN CURJNMSGPBXOGK-UHFFFAOYSA-N 0.000 claims description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 claims description 2
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical compound OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- PRNMXSACOXQQRF-UHFFFAOYSA-N 3-amino-3-oxoprop-1-ene-2-sulfonic acid Chemical compound NC(=O)C(=C)S(O)(=O)=O PRNMXSACOXQQRF-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 239000010779 crude oil Substances 0.000 abstract description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 description 41
- 239000003921 oil Substances 0.000 description 30
- 239000007921 spray Substances 0.000 description 18
- 230000035699 permeability Effects 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 125000001165 hydrophobic group Chemical group 0.000 description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011435 rock Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- XNYBUIUOTDPTMX-UHFFFAOYSA-N 2-(prop-2-enoylamino)hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCC(CS(O)(=O)=O)NC(=O)C=C XNYBUIUOTDPTMX-UHFFFAOYSA-N 0.000 description 1
- ZJCOXZXHUMVTTE-UHFFFAOYSA-N 2-(prop-2-enoylamino)tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCC(CS(O)(=O)=O)NC(=O)C=C ZJCOXZXHUMVTTE-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001856 aerosol method Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a microspheric double-comb block polymer profile control and flooding agent and a preparation method thereof. The preparation method comprises preparing an aqueous solution from an acrylamide monomer, long-chain alkylene oxide, acrylamide sulfonate and an acrylic acid monomer, adding a pH regulator, and regulating the pH value to 6-8; introducing nitrogen at the temperature of 0-15 ℃, adding a redox composite initiator, and polymerizing for 3-10 h; hydrolyzing at 70-90 deg.C water bath temperature for 1-4 h, drying at 60-90 deg.C for 4-8 h, pulverizing, and sieving; dissolving in lipophilic solvent, and stirring at 20-35 deg.C in water bath for 1-4 hr; heating to 40-50 deg.C, granulating to obtain microspheric double-comb block polymer modifying and flooding agent. The invention also provides the microspheric double-comb block polymer profile control and flooding agent prepared by the method. The microspheric double-comb block polymer profile control agent has good adaptability to a reservoir stratum, can effectively enter deep stratum, realizes high-efficiency profile control effect, and greatly improves the crude oil recovery ratio.
Description
Technical Field
The invention relates to a profile control agent and a preparation method thereof, in particular to a microspherical hydrophilic-hydrophobic double-comb type block high-molecular polymer profile control agent with controllable swelling time and a preparation method thereof, belonging to the technical field of high-molecular polymer preparation.
Background
With the increasing pace of oil field exploitation, most oil fields in China and even in the world have already entered a high water content stage, which provides new requirements and challenges for further improving the oil recovery efficiency.
At present, water injection well profile control and flooding and oil well water plugging technologies become important technical means for tertiary oil recovery, and are also indispensable supporting technologies for improving the water injection development effect of an oil field, realizing stable production of an oil reservoir and improving the crude oil recovery efficiency.
The research on the profile control and flooding agent is becoming extensive at present, and the existing profile control and flooding agent comprises a chromium and zirconium gel system, a phenolic resin system, a clay/cement dispersion, lime cream and a water swelling body which are used for a high-permeability oil layer; it is suitable for silicic acid and aluminum hydroxide gel microspheres in low permeability oil layer.
However, after long-term field application, most of the conventional modifying and flooding agents have large initial particle size, short crosslinking time, excessively high tackifying speed and excessively poor fluidity, so that the modifying and flooding agents begin to swell before being injected into a well pipe and are difficult to convey to a deeper stratum. Even if the water plugging agent enters the stratum, the water plugging particles are extruded to be broken by stratum shearing force and sieve pipes in the pumping process due to the fact that the water plugging agent expands in advance in the ground liquid distribution tank, and then the water plugging and water flow control capacity is lost.
Therefore, the traditional water plugging profile control agent can only play a profile control role at a position which is shallow from a water injection well, and is difficult to penetrate into the stratum. The deep profile control and flooding technology for high permeability oil fields still needs further research.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a profile control and flooding agent which has the advantages of proper initial particle size, long crosslinking time, moderate tackifying speed, and strong fluidity and salt resistance and is suitable for the deep profile control and flooding of a high-permeability high-salt oil layer.
In order to achieve the technical purpose, the invention provides a preparation method of a microspherical double-comb block polymer profile control and flooding agent, which comprises the following steps:
the method comprises the following steps: preparing an acrylamide monomer, long-chain alkylene oxide, acrylamide sulfonate and an acrylic acid monomer into an aqueous solution with the mass concentration of 5-40%, adding a pH regulator, and regulating the pH value to 6-8 to obtain a solution; wherein, the mixing proportion of the acrylamide monomer, the long-chain alkylene oxide, the acrylamide sulfonate and the acrylic acid monomer is 30-80: 5-30: 5-40: 1 to 20;
step two: introducing nitrogen into the solution at 0-15 ℃ for 20-60 min, adding a redox composite initiator, and polymerizing for 3-10 h to obtain a colloidal product; wherein, the process of the second step keeps the introduction of nitrogen; the addition amount of the redox composite initiator is 0.2-0.5% of the total mass of the monomers, the total mass of the monomers refers to the total mass of aqueous solutions prepared from acrylamide monomers, long-chain alkylene oxides, acrylamide sulfonate and acrylic acid monomers, and the mass of the monomers does not contain water;
step three: hydrolyzing the colloidal product at 70-90 ℃ in a water bath for 1-4 h, drying at 60-90 ℃ for 4-8 h, crushing and sieving to obtain double comb type block copolymer powder; wherein, the selected mesh screen is 400-800 mesh;
step four: dissolving the double comb type block copolymer powder in a lipophilic solvent, and stirring for 1-4 h at the water bath temperature of 20-35 ℃ to obtain emulsion; wherein, the powdery double comb type block copolymer powder is dissolved in the lipophilic solvent with the concentration of 100ppm to 2000ppm, and the stirring speed is 50rad/min to 200 rad/min;
step five: heating the emulsion to 40-50 ℃, and granulating by aerosol equipment to obtain the microspherical double-comb block polymer profile control and flooding agent.
In the preparation method of the microspheric double-comb block polymer profile control and flooding agent, preferably, the long-chain alkylene oxide used comprises one or more of the combination of epoxy hexane, epoxy octane, 1, 2-epoxy dodecane and 1, 2-epoxy tetradecane. In the preparation method of the microspherical double-comb block polymer profile control and flooding agent, the adopted acrylamide sulfonate preferably comprises one or more of 2-acrylamide-2-methyl propane sulfonic acid, 2-acrylamide tetradecane sulfonic acid and 2-acrylamide hexadecane sulfonic acid, and the raw materials are all provided by Bailingwei science and technology Limited.
According to the specific embodiment of the invention, in the preparation method of the microspherical double-comb block polymer profile control agent, the adopted nitrogen is high-purity nitrogen with the purity of 99.999 percent, and when the nitrogen is introduced, the oxygen can be isolated and the mixed reaction solution can not be sprayed out.
In the preparation method of the microspheric double-comb block polymer profile control and flooding agent, preferably, the pH regulator used comprises one or more of sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, monoethanolamine, diethanolamine, triethanolamine and ammonia water.
In the preparation method of the microspherical double-comb block polymer profile control and flooding agent, preferably, the redox composite initiator comprises the following raw materials of persulfate, bisulfite, amine compound and the balance of water, wherein the mass ratio of the persulfate to the bisulfite to the amine compound is 0.2-20 wt%, based on the total mass of the redox composite initiator being 100 wt%: 0.1 wt% -10 wt%: 0.1 wt% -30 wt%.
In the preparation method of the microspheric double-comb block polymer profile control and flooding agent, preferably, the persulfate used comprises ammonium persulfate, sodium persulfate or potassium persulfate.
In the preparation method of the microspheric double-comb block polymer profile control agent, preferably, the bisulfite used comprises ammonium bisulfite, sodium bisulfite or potassium bisulfite.
In the preparation method of the microspheric double-comb block polymer profile control and flooding agent, preferably, the amine compound used comprises one or a combination of several of N, N-diethylethylenediamine, diethylenetriamine, N, N, N ', N' -tetraethylethylenediamine, N, N-diisopropylethylenediamine and N, N, N ', N' -tetraallylethylenediamine.
In the preparation method of the microspheric double-comb block polymer profile control and flooding agent, the lipophilic solvent adopted preferably comprises n-hexane, cyclohexane, benzene, toluene, carbon tetrachloride or chlorobenzene.
The invention also provides a microspheric double-comb block polymer profile control and flooding agent which is prepared by the preparation method of the microspheric double-comb block polymer profile control and flooding agent.
In the microspheric double-comb block polymer profile control and flooding agent provided by the invention, the particle size of the microspheric double-comb block polymer profile control and flooding agent is preferably 2-8 μm.
The invention also provides an aerosol device, which is used in the preparation method of the microspheric double-comb block polymer profile control agent, and the aerosol device comprises:
the device comprises a mother liquor tank, a spray gun, a first screening tower, a second screening tower, a third screening tower, a blower and a draught fan;
the mother liquor tank is communicated with the first screening tower, and a spray gun is arranged between the mother liquor tank and the first screening tower;
the first screening tower, the second screening tower and the third screening tower are communicated in sequence;
the blower is communicated with the first screening tower;
and the induced draft fan is communicated with the third screening tower.
In the aerosol equipment provided by the invention, the adopted spray guns comprise a single spray gun, three spray guns, four spray guns, six spray guns or eight spray guns. The evaporation capacity and thus the spray gun, is chosen according to the porosity requirements of the substrate and can be chosen by the person skilled in the art as the case may be.
In the aerosol equipment provided by the invention, the gun head of the spray gun is arranged at the upper end of the inside of the first screening tower.
The preparation method of the microspheric double-comb block polymer profile control and flooding agent provided by the invention comprises the following steps: acrylamide, acrylic acid, long-chain alkylene oxide and acrylamide sulfonate are copolymerized to form the hydrophilic-hydrophobic block type water-soluble high polymer. The acrylamide sulfonate is used as a multifunctional anionic monomer and has good polymerization activity, and two S-O coordination bonds contained in a sulfonic acid group in the acrylamide sulfonate can effectively block the attack of external cations, so that the temperature resistance and salt resistance of the polymer are improved; carboxylate ions (-COOH) in the Acrylic Acid (AA) can obviously improve the solubility of the polymer in water and increase the dissolution speed; the hydrophobic group is alkylene oxide with long branched chain structure, and after the length of alkyl carbon chain is greater than 6, the required hydrophobic degree can be realized, the alkylene oxide belongs to three-membered ring, and because of its large tension and the polar action of C-O bond, the ring opening can be realized by C-O bond breaking in acid (cation), alkali (anion) and neutral (water), the ring opening polymerization product of the alkylene oxide is polyether, and mainly acts on the prepolymer of the nonionic surfactant. Wherein, the long-chain alkane side group after ring opening and blocking is used as a main body hydrophobic group.
The microspherical double-comb block polymer profile control agent has micron-sized initial particle size, and the outer layer is taken as a protective film by long-chain hydrophobic alkyl, so that the deformed ball can smoothly go deep into the stratum, and with the extension of the dissolution time in simulated saline, water molecules gradually penetrate through the pore passage of the deformed ball, enter the block copolymer wrapped by the hydrophobic alkyl chain, contact with hydrophilic groups, and cause the annular chain to gradually swell and finally be completely opened. The hydrophilic groups are completely exposed in the saline water, and the hydrophobic groups begin to gather due to the hydrophobic effect, so that the association between polymer chains occurs to form a dynamic physical cross-linking network, thereby leading the hydrodynamic volume to be increased, greatly improving the solution viscosity, further plugging a high-permeability flow channel in a water injection stratum, and realizing the purposes of oil stabilization and water control. Compared with the traditional oil displacement agent, the oil displacement capacity of the oil displacement agent is greatly improved.
The preparation method of the microspheric double-comb block polymer profile control and flooding agent provided by the invention can reasonably and effectively control the plugging time through the design of molecular scale and macroscopic scale, and simultaneously solves the problems of poor plugging property, poor temperature resistance, no salt resistance and the like of the profile control and flooding agent.
The microspherical double-comb block polymer profile control and flooding agent provided by the invention is a hydrophilic-hydrophobic block graft spherical polymer, the outward side group is a hydrophobic group, and the hydrophilic group is also used as a side group to be orderly and inwards arranged to form a micron-sized controllable-solubility type deformation ball. Meanwhile, the particle size of the microspheric double-comb block polymer profile control and flooding agent is controlled to be 2-8 mu m by an aerosol process.
The preparation method of the microspheric double-comb block polymer profile control and flooding agent provided by the invention has simple preparation process flow; the microspheric double-comb block polymer profile control agent provided by the invention is a deformable material with controllable swelling time, and solves the problems of poor profile control and blocking performance, no temperature resistance, no salt resistance and the like of the existing profile control agent.
The microspheric double-comb type block polymer profile control agent provided by the invention has micron-sized initial particle size and a 'protective film' wrapped by a hydrophobic group shell layer, so that the profile control agent and a reservoir have good adaptability, can effectively enter deep stratum, controllably adjusts the swelling time per se, realizes a high-efficiency profile control effect, and greatly improves the crude oil recovery ratio.
Drawings
Fig. 1 is a schematic structural view of an aerosol device according to embodiment 1.
FIG. 2 is a plot of the apparent viscosity of the microspherical double comb block polymer profile control agent of example 6 as a function of time.
Description of the main figures
1 mother liquor tank 2 spray gun 3 first screening tower 4 second screening tower 5 third screening tower 6 air blower 7 induced draft fan 8 column pump plug
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The present embodiment firstly provides an aerosol apparatus, the structure of which is shown in fig. 1, and the aerosol apparatus includes:
the device comprises a mother liquor tank 1, three spray guns 2, a first screening tower 3, a second screening tower 4, a third screening tower 5, a blower 6 and a draught fan 7;
the mother liquor tank 1 is communicated with the first screening tower 3, and a spray gun 2 is arranged between the mother liquor tank 1 and the first screening tower 3; a plunger pump 8 is arranged on the spray gun 2; the first screening tower 3, the second screening tower 4 and the third screening tower 5 are communicated in sequence; the blower 6 is communicated with the first screening tower 3; the induced draft fan 7 is communicated with the third screening tower 5; the tip of the lance 2 is arranged at the upper end inside the first sieving tower 3.
The embodiment provides a preparation method of a microspherical double-comb block polymer profile control and flooding agent, which specifically comprises the following steps:
(1) preparing a solution: in molar parts, preparing an acrylamide monomer and cyclohexene oxide into a 30% aqueous solution by mixing a 2-acrylamido-2-methylpropanesulfonic acid monomer and acrylic acid according to a ratio of 40:25:12:7, adding a pH regulator (sodium hydroxide and diethanolamine), and regulating the pH to 7;
(2) the polymerization process comprises the following steps: continuously introducing 99.999% of high-purity nitrogen at the constant temperature of 5 ℃, sequentially adding a redox composite initiator (consisting of N, N-diethyldiamine, sodium persulfate and sodium bisulfite with the mass ratio of 7:5:1) after 50min, continuously introducing the high-purity nitrogen in the process, wherein the addition amount of the redox composite initiator is 0.3% of the total mass of monomers (the monomers refer to the monomer sum of 30% aqueous solution prepared from acrylamide monomer and epoxy hexane, and do not contain water), continuously introducing the high-purity nitrogen for 60min after adding the redox composite initiator, sealing, and reacting for 4h under a sealed condition to obtain a rubber block;
(3) and (3) performing rubber block post-treatment: stirring the rubber blocks, curing at 80 ℃ for 1.5h, drying at 60 ℃ for 6h, then crushing and screening, and selecting a mesh screen with 500 meshes for screening to obtain double comb type block copolymer powder;
(4) preparing micro-spherical profile control agent emulsion: dissolving the double-comb block copolymer powder in a lipophilic solvent of n-hexane at the concentration of 500ppm, and stirring for 3 hours at the water bath temperature of 30 ℃ at the stirring speed of 150rad/min to obtain emulsion;
(5) granulation of the polymer: preheating the emulsion to 40 ℃, and granulating by the aerosol equipment to finally obtain the microspherical double-comb block polymer profile control and flooding agent with the serial number TQ-1.
The granulation by the aerosol equipment specifically comprises the following steps:
preheating the emulsion in the mother liquor tank 1 to 40 ℃, and feeding the emulsion into the spray gun 2 from the mother liquor tank 1 under the action of the plunger pump 8; the spray head on the top of the tower sprays the atomized particles into a first screening tower 3 in a mist form at an atomization angle of 50-80 ℃, meanwhile, filtered air enters the first screening tower 3 through an air blower 6, uniformly distributed hot air and atomized materials in the tower perform sufficient heat exchange, water is evaporated after heat exchange and is greatly rotated at 180 ℃, the atomized materials discharged from the top sequentially enter a second screening tower 4 and a third screening tower 5, dry materials are powdery and fall into the bottom of the first screening tower 3, the atomized materials discharged from the top of the third screening tower 5 enter a fluidized bed through a vibrating screen, fine powder particles subjected to boiling heating and cooling enter a collecting tank through a vibrating screen, and finished products are collected to obtain the microspherical double-comb block polymer profile control and flooding agent. The surfaces of a mother liquor tank 1, a spray gun 2, a first screening tower 3, a second screening tower 4 and a third screening tower 5 in the aerosol equipment are all covered with heat-insulating layers, and the granulation process is carried out in a constant temperature environment.
Example 2
The embodiment provides a preparation method of a microspherical double-comb block polymer profile control and flooding agent, which specifically comprises the following steps:
(1) preparing a solution: in molar parts, preparing an aqueous solution with the concentration of 28% by using acrylamide monomers, epoxyoctane, 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid monomers according to the proportion of 50:23:19:7, adding a pH regulator (sodium bicarbonate), and regulating the pH to 7.5;
(2) the polymerization process comprises the following steps: continuously introducing 99.999% of high-purity nitrogen at a constant temperature of 12 ℃, sequentially adding a redox composite initiator (consisting of diethylenetriamine, potassium persulfate and potassium bisulfite with the mass ratio of 3:2:1) after 40min, continuously introducing the high-purity nitrogen in the process, wherein the addition amount of the redox composite initiator is 0.25% of the total mass of monomers (the monomers refer to the sum of the monomers in an aqueous solution with the concentration of 28% and prepared from acrylamide monomers and cyclohexene oxide, and do not contain water), continuously introducing the high-purity nitrogen for 60min after adding the redox composite initiator, sealing, and reacting for 3h under a sealed condition to obtain a rubber block;
(3) and (3) performing rubber block post-treatment: stirring the rubber blocks, curing at 85 ℃ for 2h, drying at 85 ℃ for 5h, then crushing and screening, and selecting a 600-mesh screen for screening to obtain double comb type block copolymer powder;
(4) preparing micro-spherical profile control agent emulsion: dissolving the double comb type block copolymer powder in a lipophilic solvent of n-hexane at a concentration of 1000ppm, and stirring for 2.5h at a water bath temperature of 30 ℃ and a stirring speed of 150rad/min to obtain an emulsion;
(5) granulation of the polymer: the emulsion was preheated to 40 ℃ and granulated by the aerosol apparatus of example 1 to produce the microspheroidal double comb block polymer profile control agent, numbered TQ-2.
Example 3
The embodiment provides a preparation method of a microspherical double-comb block polymer profile control and flooding agent, which specifically comprises the following steps:
(1) preparing a solution: in molar parts, preparing an aqueous solution with the concentration of 35% by using acrylamide monomers, 1, 2-epoxydodecane, 2-acrylamidotetradecane sulfonic acid and acrylic acid monomers according to the proportion of 45:25:12:5, adding a pH regulator (sodium bicarbonate), and regulating the pH to 7;
(2) the polymerization process comprises the following steps: continuously introducing 99.999% of high-purity nitrogen at the constant temperature of 15 ℃, sequentially adding a redox composite initiator (consisting of N, N, N ', N' -tetraethylethylenediamine, ammonium persulfate and ammonium bisulfite with the mass ratio of 4:2:1) after 30min, continuously introducing the high-purity nitrogen in the process, wherein the addition amount of the redox composite initiator is 0.4% of the total mass of monomers (the monomers refer to the sum of the monomers in an aqueous solution with the concentration of 35% and contain no water prepared from acrylamide monomers and epoxy hexane), continuously introducing the high-purity nitrogen after 45min after adding the redox composite initiator, sealing, and reacting for 2.5h under a sealed condition to obtain a rubber block;
(3) and (3) performing rubber block post-treatment: stirring the rubber blocks, curing at 90 ℃ for 2.5h, drying at 90 ℃ for 2h, then crushing and screening, and selecting a mesh screen of 700 meshes for screening to obtain double comb type block copolymer powder;
(4) preparing micro-spherical profile control agent emulsion: dissolving the double comb type block copolymer powder in a lipophilic solvent of n-hexane at a concentration of 600ppm, and stirring for 2.5h at a water bath temperature of 25 ℃ and a stirring speed of 180rad/min to obtain emulsion;
(5) granulation of the polymer: preheating the emulsion to 40 ℃, and granulating by an aerosol device to finally obtain the microspheric double-comb block polymer profile control and flooding agent with the serial number of TQ-3.
Example 4
The embodiment provides a preparation method of a microspherical double-comb block polymer profile control and flooding agent, which specifically comprises the following steps:
(1) preparing a solution: preparing an acrylamide monomer, 1, 2-epoxytetradecane and 2-acrylamidohexadecane sulfonic acid monomer into a 40% aqueous solution according to a ratio of 7:3:2:1 in parts by mole, adding a pH regulator (sodium bicarbonate), and regulating the pH to 6.5;
(2) the polymerization process comprises the following steps: continuously introducing 99.999% of high-purity nitrogen at a constant temperature of 12 ℃, sequentially adding a redox composite initiator (consisting of N, N, N ', N' -tetraallylethylenediamine, sodium persulfate and sodium bisulfite with the mass ratio of 11:6:3) after 40min, continuously introducing the high-purity nitrogen in the process, wherein the addition amount of the redox composite initiator is 0.3% of the total mass of monomers (the monomers refer to the sum of the monomers in an aqueous solution with the concentration of 40% and contain no water prepared from acrylamide monomers and epoxy hexane), continuously introducing the high-purity nitrogen after 60min after adding the redox composite initiator, sealing, and reacting for 3h under a sealed condition to obtain a rubber block;
(3) and (3) performing rubber block post-treatment: stirring the rubber blocks, curing at 80 ℃ for 4h, drying at 80 ℃ for 5h, then crushing and screening, and selecting a mesh screen of 800 meshes for screening to obtain double comb type block copolymer powder;
(4) preparing micro-spherical profile control agent emulsion: dissolving the double comb type block copolymer powder in a lipophilic solvent of n-hexane at a concentration of 600ppm, and stirring for 4h at a water bath temperature of 35 ℃ and a stirring speed of 200rad/min to obtain an emulsion;
(5) granulation of the polymer: preheating the emulsion to 50 ℃, and granulating by an aerosol device to finally obtain the microspheric double-comb block polymer profile control and flooding agent with the serial number of TQ-4.
Example 5
At a total mineralization of 1.28X 105mg/L of simulated saline with the total concentration of calcium and magnesium ions being 425mg/L is added with the microspherical double-comb block polymer profile control agent of the embodiment 1 to the embodiment 4 to prepare polymer saline solution with the concentration being 500 mg/L. The test result of the laser particle sizer shows that the material can be directly and rapidly dispersed in simulated saline, the particle size is controlled to be 2-8 mu m, and the result is shown in table 1.
TABLE 1
| Sample numbering | TQ-1 | TQ-2 | TQ-3 | TQ-4 |
| Particle size/. mu.m | 8.0 | 7.8 | 3.3 | 2.2 |
Example 6
This example shows that the apparent viscosity of the microspherical double comb-type block polymer profile control agent of examples 1-4 is measured, and the total mineralization of the polymer saline solution with the concentration of 1500mg/L is 1.28 multiplied by 10 at 120 DEG C57.34s in simulated saline water with the total concentration of calcium and magnesium ions of 425mg/L-1The initial apparent viscosity was 11.6 mPas. Over time, water molecules penetrate through the microsphere polymer encapsulated by the hydrophobic groups to combine with the hydrophilic groups inside the sphere centerAnd finally, the microspherical material is completely opened, so that the stretched block copolymer with the hydrophilic-hydrophobic groups is formed. -SO in Block copolymers after chain end opening3The Na group can effectively isolate divalent cations and inhibit Ca2+With Mg2+The ions are combined with the profile control agent to prevent molecular chain breakage and sedimentation inactivation, and the excellent salt resistance is shown. The continuous test shows that the apparent viscosity is rapidly increased to 25.7 mPas within 3h to 9h, and the viscosity is kept stable within 96h, and the result is shown in figure 2. The results of fig. 2 show that the viscosity of the microspherical double comb block polymer profile control and flooding agent of examples 1-4 is slowly increased in the process of going deep into the stratum, and finally the viscosity can be increased to about 2.2 times of the original viscosity, and the microspherical double comb block polymer profile control and flooding agent has micron-sized initial particle size and can smoothly enter the stratum.
In addition, it is noted that the dissolution rate of the microspherical double comb block polymer profile control agent of examples 1-4 is inversely related to the proportion of hydrophobic groups. Wherein, the proportion of hydrophobic groups in the TQ-1 and TQ-3 profile control and flooding agents is respectively 26.6 percent and 25.8 percent; the proportion of hydrophobic groups in the profile control agent TQ-2 and the profile control agent TQ-4 is respectively 19.2 percent and 20 percent. As can be seen from FIG. 2, the slopes of TQ-2 and TQ-4 are significantly greater than those of TQ-1 and TQ-3 in 0-9 days, i.e., the former dissolution rate is significantly faster than the latter.
Example 7
In this example, the microspherical double-comb block polymer profile control and flooding agent of examples 1 to 4 was tested for aging resistance, and the specific process is as follows:
firstly, fresh sample viscosity test: adopting Kazakhstan hypersalinity simulation water: the total degree of mineralization is 1.28X 105mg/L, total concentration of calcium and magnesium ions was 425mg/L, and the microspherical double comb-type block polymer profile control and flooding agent of examples 1-4 was diluted to 1500ppm concentration, measured at 85 deg.C, 7.34cm-1Viscosity of the sample at a rotational speed;
secondly, aging treatment is carried out: vacuumizing, and sealing at 120 deg.C under oxygen-free condition for 90 days;
thirdly, testing the viscosity of the aged sample: taking out the sample, standing at normal temperature, and testing the constant temperature at 85 deg.C and 7.34cm-1The aged viscosity of the sample at the rotational speed;
fourthly, the viscosity retention calculation ═ (fresh sample viscosity-aged sample viscosity)/fresh sample viscosity × 100%. The test results are shown in table 2.
The results in Table 2 show that the viscosity retention of the microspherical double comb block polymer profile control and flooding agent of examples 1-4 can reach 90-96% after being aged for 90 days at 120 ℃ under the anaerobic condition.
Table 2 examples 1-4 sample viscosity retention
Example 8
In this example, a simulated core flooding test was performed on the microspherical double-comb block polymer profile control and flooding agent of examples 1 to 4.
A,
Core sampling: sampling a rock core of a certain block of the Kazakhstan oil field, wherein the rock core is 25cm in length and 3.5cm in diameter;
kazakhstan hypersalinity simulation water: the total degree of mineralization is 1.28X 105mg/L, wherein the total concentration of calcium and magnesium ions is 425 mg/L;
determination of water phase permeability before plugging: vacuumizing the core, injecting high-salinity saline water of Kazakhstan into the core until the core is saturated, driving the core with water at a flow rate of 1L/min until the pressure is stable, and measuring the water phase permeability of the core to be 189 multiplied by 103μm2；
Simulating a core oil displacement test: injecting dehydrated crude oil in a certain block of the Kazakhstan oil field at a constant temperature of 120 ℃, performing saturation treatment on the core, and performing water drive for 24 hours until the core is in a residual oil state;
injecting 2PV the microspheric double-comb block polymer profile control and flooding agent TQ-1 of example 1, keeping the temperature at 120 ℃ for 72h, continuing to displace with the highly mineralized saline water of Kazakhstan, and measuring that the water phase permeability after plugging is 5.2 multiplied by 103μm2The plugging rate was calculated to be 97.2%.
II,
Core sampling: sampling a rock core of a certain block of the Kazakhstan oil field with the length of 30cm and the diameter of 4.0 cm;
kazakhstan hypersalinity simulation water: the total degree of mineralization is 1.28X 105mg/L, wherein the total concentration of calcium and magnesium ions is 425 mg/L;
determination of water phase permeability before plugging: vacuumizing the core, injecting high salinity saline water of Kazakhstan into the core until the core is saturated, driving the core with water at a flow rate of 1L/min until the pressure is stable, and measuring the water phase permeability of the core to be 201 multiplied by 103μm2；
Simulating a core oil displacement test: injecting dehydrated crude oil in a certain block of the Kazakhstan oil field at the constant temperature of 110 ℃, performing saturation treatment on the core, and performing water flooding for 24 hours until the core is in a residual oil state;
2PV the microspheric double comb block polymer control agent TQ-2 of example 2 was injected and the temperature was maintained at 110 ℃ for 72 hours. And continuously displacing with high salinity brine of Kazakhstan, and measuring the water phase permeability after plugging to be 2.6 multiplied by 103μm2The plugging rate was calculated to be 98.7%.
III,
Core sampling: sampling a rock core of a certain block of the Kazakhstan oil field, wherein the rock core has the sampling length of 27cm and the diameter of 3.8 cm;
kazakhstan hypersalinity simulation water: the total degree of mineralization is 1.28X 105mg/L, wherein the total concentration of calcium and magnesium ions is 425 mg/L;
determination of water phase permeability before plugging: vacuumizing the core, injecting high-salinity saline water of Kazakhstan into the core until the core is saturated, driving the core with water at a flow rate of 1L/min until the pressure is stable, and measuring the water phase permeability of the core to be 197 multiplied by 103μm2；
Simulating a core oil displacement test: injecting dehydrated crude oil in a certain block of the Kazakhstan oil field at the constant temperature of 85 ℃, performing saturation treatment on the core, and performing water flooding for 24 hours until the core is in a residual oil state;
the microspherical double comb block polymer control agent TQ-3 of example 3 was injected into the reactor and the temperature was maintained at 85 ℃ for 72 hours. And continuously displacing with high salinity brine of Kazakhstan, and measuring the water phase permeability after plugging to be 3.1 multiplied by 103μm2The plugging rate was calculated to be 98.5%.
Fourthly,
Core sampling: sampling a rock core of a certain block of the Kazakhstan oil field, wherein the rock core has the sampling length of 33cm and the diameter of 4.1 cm;
kazakhstan hypersalinity simulation water: the total degree of mineralization is 1.28X 105mg/L, wherein the total concentration of calcium and magnesium ions is 425 mg/L;
determination of water phase permeability before plugging: vacuumizing the core, injecting high salinity saline water of Kazakhstan into the core until the core is saturated, driving the core with water at a flow rate of 1L/min until the pressure is stable, and measuring the water phase permeability of the core to be 176 multiplied by 103μm2；
Simulating a core oil displacement test: injecting dehydrated crude oil in a certain block of the Kazakhstan oil field at the constant temperature of 95 ℃, performing saturation treatment on the core, and performing water flooding for 24 hours until the core is in a residual oil state;
the microspherical double comb block polymer control agent TQ-4 of example 4 was injected into the reactor and the temperature was maintained at 95 ℃ for 72 hours. And continuously displacing with high salinity brine of Kazakhstan, and measuring the water phase permeability after plugging to be 2.1 multiplied by 103μm2The plugging rate was calculated to be 98.8%.
The above examples illustrate that the preparation process of the preparation method of the microspherical double-comb block polymer profile control and flooding agent of the present invention is simple; the microspheric double-comb type block polymer profile control and flooding agent has micron-sized initial particle size, has good adaptability to a reservoir stratum, can effectively enter deep stratum, controllably adjusts the swelling time per se, realizes high-efficiency profile control and flooding effect, and greatly improves the crude oil recovery rate.
Claims (8)
1. A preparation method of a microspheric double-comb block polymer profile control and flooding agent comprises the following steps:
the method comprises the following steps: preparing an acrylamide monomer, long-chain alkylene oxide, acrylamidosulfonic acid and an acrylic acid monomer into an aqueous solution with the mass concentration of 5-40%, adding a pH regulator, and regulating the pH value to 6-8 to obtain a solution; wherein, the mixing proportion of the acrylamide monomer, the long-chain alkylene oxide, the acrylamido sulfonic acid and the acrylic acid monomer is 30-80: 5-30: 5-40: 1 to 20; the long-chain alkylene oxide comprises one or a combination of more of epoxy hexane, epoxy octane, 1, 2-epoxy dodecane and 1, 2-epoxy tetradecane; the acrylamide sulfonic acid comprises one or a combination of more of 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide tetradecane sulfonic acid and 2-acrylamide hexadecane sulfonic acid;
step two: introducing nitrogen into the solution at 0-15 ℃ for 20-60 min, adding a redox composite initiator, and polymerizing for 3-10 h to obtain a colloidal product; wherein, the process of the second step keeps the introduction of nitrogen; the addition amount of the redox composite initiator is 0.2-0.5% of the total mass of the monomers, the total mass of the monomers refers to the total mass of aqueous solutions prepared from acrylamide monomers, long-chain alkylene oxides, acrylamido sulfonic acid and acrylic acid monomers, and the mass of the monomers does not contain water;
step three: hydrolyzing the colloidal product at 70-90 ℃ in a water bath for 1-4 h, drying at 60-90 ℃ for 4-8 h, crushing and sieving to obtain double comb type block copolymer powder; wherein, the selected mesh screen is 400-800 mesh;
step four: dissolving the double comb type block copolymer powder in a lipophilic solvent, and stirring for 1-4 h at the water bath temperature of 20-35 ℃ to obtain an emulsion; wherein the powdery double comb type block copolymer powder is dissolved in a lipophilic solvent at the concentration of 100ppm-2000ppm, and the stirring speed is 50rad/min-200 rad/min;
step five: and heating the emulsion to 40-50 ℃, and granulating by using aerosol equipment to obtain the microspherical double-comb block polymer profile control and flooding agent.
2. The method of claim 1, wherein the pH modifier comprises one or more of sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, monoethanolamine, diethanolamine, triethanolamine, and ammonia in combination.
3. The preparation method of the microspherical double-comb block polymer profile control and flooding agent as claimed in claim 1, wherein the redox composite initiator comprises a persulfate, a bisulfite, an amine compound and the balance of water, wherein the mass ratio of the persulfate, the bisulfite and the amine compound is 0.2-20 wt%: 0.1 wt% -10 wt%: 0.1 wt% -30 wt%.
4. The method for preparing the microspheric double-comb block polymer profile control and flooding agent according to claim 3, wherein the persulfate comprises ammonium persulfate, sodium persulfate or potassium persulfate, and the bisulfite comprises ammonium bisulfite, sodium bisulfite or potassium bisulfite.
5. The method for preparing the microspheric double comb-type block polymer profile control agent according to claim 3, wherein the amine compound comprises one or more of N, N-diethylethylenediamine, diethylenetriamine, N, N, N ', N' -tetraethylethylenediamine, N, N-diisopropylethylenediamine and N, N, N ', N' -tetraallylethylenediamine.
6. The method of claim 1, wherein the lipophilic solvent comprises n-hexane, cyclohexane, benzene, toluene, carbon tetrachloride or chlorobenzene.
7. A microspheric double comb type block polymer profile control and flooding agent, which is prepared by the preparation method of the microspheric double comb type block polymer profile control and flooding agent as claimed in any one of claims 1 to 6.
8. The microspheroidal double comb block polymer profile control agent according to claim 7, wherein the microspheroidal double comb block polymer profile control agent has a particle size of from 2 μm to 8 μm.
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