CN103965852B - Containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method - Google Patents
Containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method Download PDFInfo
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- CN103965852B CN103965852B CN201310044451.0A CN201310044451A CN103965852B CN 103965852 B CN103965852 B CN 103965852B CN 201310044451 A CN201310044451 A CN 201310044451A CN 103965852 B CN103965852 B CN 103965852B
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- displacement agent
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 83
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 38
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 241000158728 Meliaceae Species 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- KHBQMWCZKVMBLN-IDEBNGHGSA-N benzenesulfonamide Chemical group NS(=O)(=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 KHBQMWCZKVMBLN-IDEBNGHGSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005728 strengthening Methods 0.000 abstract description 5
- 150000001412 amines Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 100
- 238000011084 recovery Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 15
- 239000011435 rock Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 230000003213 activating effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WSVQZZFFMBFCKH-UHFFFAOYSA-N [Na].C(CCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O Chemical compound [Na].C(CCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O WSVQZZFFMBFCKH-UHFFFAOYSA-N 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 101100317264 Caenorhabditis elegans wts-1 gene Proteins 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 pyridine radicals cation Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 201000008827 tuberculosis Diseases 0.000 description 2
- IYZKEAIYJSVBRR-UHFFFAOYSA-N C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] Chemical compound C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] IYZKEAIYJSVBRR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 102100024233 High affinity cAMP-specific 3',5'-cyclic phosphodiesterase 7A Human genes 0.000 description 1
- 101001117267 Homo sapiens High affinity cAMP-specific 3',5'-cyclic phosphodiesterase 7A Proteins 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- XVLCKYSFEKQTNU-UHFFFAOYSA-N [S].C(CCCCCCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound [S].C(CCCCCCCCCCCCCCCCC)C1=CC=CC=C1 XVLCKYSFEKQTNU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- ZIGVUIYVPLQEAL-UHFFFAOYSA-M sodium;2-tetradecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O ZIGVUIYVPLQEAL-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C09K8/584—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 surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method, the problem mainly solving the compound oil displacement agent oil displacement efficiency difference used in prior art.The present invention is by using containing polymer and the compound oil displacement agent of negative and positive system surfactant, including negative and positive system surfactant, polymer and water；Described negative and positive system surfactant by anion surfactant and cationic surfactant with mol ratio (1 ~ 100): 1 forms；Described anion surfactant is any one in sulfonate, carboxylate or phosphate；Described cationic surfactant is quaternary ammonium salt or quaternary amine alkali；Described polymer is modified polyacrylamide, formed by acrylamide, 2 two kinds of monomer copolymerizations of acrylamido 2 methyl propane sulfonic acid, in modified polyacrylamide, two kinds of monomeric units mole is (1 ~ 4): the technical scheme of 1, preferably solve this problem, can be used in the strengthening displacement of reservoir oil production of high-temperature low salt type oil reservoir.
Description
Technical field
The present invention relates to containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method.
Background technology
Chemical flooding is the main method of the strengthening displacement of reservoir oil.As an important technology in chemical flooding, polymer, surface activity
The ASP Oil-Displacing Technology that agent and alkali are formed has carried out some field tests in China and foreign countries, achieves good oil displacement efficiency.
But the addition of alkali causes easily causing oil layer blocking, permeability decrease in field test, and emulsification of crude oil is serious, Produced Liquid
Profit is difficult to separate.Owing to not using alkali in the binary combination flooding formula that polymer and surfactant are formed, effectively prevent
The problems referred to above and draw attention, but due to need not any alkali, the interfacial tension between crude oil, water is often unable to reach ultralow value,
Thus have impact on oil displacement efficiency, it is therefore desirable to research and development high-efficient oil-displacing agent.According to the formula Er=E improving oil recovery factor
υ Ed understands, and Ed represents that surfactant flooding improves oil recovery factor, and its mechanism of action is that the interface reduced between profit is opened
Power；E υ represents that polymer flooding improves oil recovery factor, and its mechanism of action is to increase sweep efficiency, in poly-table binary combination flooding
Reduce oil water interfacial tension Main Function be surfactant, therefore exploitation high-efficient oil-displacing agent it is crucial that exploitation and polymer
Compatibility and the most excellent surfactant of interface performance.
Surfactant for EOR has anion surfactant, such as petroleum sulfonate, alkylsulfonate, olefin sulfonic acid at present
Salt and lignosulfonates etc..Use also having been reported that, such as Chinese patent CN 1528853, CN of cationic surfactant
1817431, CN 1066137 etc. in succession report bisamide type cationic, fluorine-containing cationic type and contain pyridine radicals cation pair
Sub-surface activating agent, but big, high in cost of production shortcoming is lost owing to cation has absorption, limit its making at Oil Field
With.The microemulsion flooding of foreign study report, as Kraft etc. has investigated under conditions of water-mineralizing degree is up to 220 g/L, 5%
The microemulsion system phase of polyoxyethylene ether alkyl sodium carboxymethyl, phase transition temperature (PIT) rule and interfacial tension, result shows, should
Surfactant does not decomposes in 3 weeks at 95 DEG C, adsorption losses 0.4 mg/g, and without obvious chromatographic isolation, but due to
Surfactant usage amount is big, cost is high, and microemulsion flooding is restricted as oil displacement agent.
Compound surfactant application in the strengthening displacement of reservoir oil is mainly anion and nonionic compound surfactant,
Addition additive alkali is generally required in using, to reach ultralow oil/water interfacial tension, but owing to non-ionic heat resistance is poor,
Often the most ineffective when high temperature.Also there is report as surfactant oil displacement after different anions surfactant compound
Lead, as Chinese patent CN1458219A discloses a kind of ultralow interface of Surfactant/Polymer binary strengthening displacement of reservoir oil application
Tension composite drives formula, the surfactant wherein used be petroleum sulfonate or with petroleum sulfonate for host add diluent and
The complexed surfactant of other surfactant compound, the percentage by weight of its component is petroleum sulfonate 50～100%, alkane
Base sulfonate 0～50%, carboxylate 0～50%, alkylaryl sulfonates 0～35%, low-carbon alcohols 0～20%, this face bioactivator activity
Difference, oil displacement efficiency are low, and surfactant system is the most complicated.
Summary of the invention
One of the technical problem to be solved is that the compound oil displacement agent used in prior art is in the strengthening displacement of reservoir oil
The problem of oil displacement efficiency difference in journey, it is provided that a kind of new containing polymer and the compound oil displacement agent of negative and positive system surfactant.Should
Oil displacement agent in the oil displacement process, has that alkali-free, corrosion-free and dirty injury, concentration be low, displacement of reservoir oil effect under the high temperature conditions
The advantage that rate is high.
The two of the technical problem to be solved are to provide and a kind of use described compound of one of above-mentioned technical problem
The flooding method of oil displacement agent.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: containing polymer and negative and positive system surface
The compound oil displacement agent of activating agent, in terms of mass fraction, including following component:
The negative and positive system surfactant of (1) 0.01～5.0 part；
The polymer of (2) 0.01～3.0 parts；
The water of (3) 90.0～99.9 parts；
Described negative and positive system surfactant by anion surfactant with quaternary ammonium cation surfactant to rub
You are than (1 ~ 100): 1 composition；Described anion surfactant is any one in sulfonate, carboxylate or phosphate, knot
Lipophilic group in structure is C8～C30Alkyl；Described cationic surfactant has C8～C30Alkyl and described cationic surface
Nitrogen-atoms in active agent structures is connected, and described cationic surfactant is quaternary ammonium salt or quaternary amine alkali；Described polymer is for changing
Property polyacrylamide, by acrylamide (be called for short AM), two kinds of monomers of 2-acrylamide-2-methylpro panesulfonic acid (being called for short AMPS) altogether
Poly-forming, in modified polyacrylamide, two kinds of monomeric units mole is (1 ~ 4): 1, and viscosity-average molecular weight is 300 ~ 10,000,000.
The surfactant of negative and positive system described in technique scheme is lived with cationic surface by anion surfactant
Property agent preferably with mol ratio (1.2 ~ 20): 1 composition.Described anion surfactant is preferably alkylbenzenesulfonate, C12~C22
Alpha-alkene sulfonate, C9~C17Carboxylate, mahogany acid, petroleum carboxylate or lignosulfonates in any one or
Mixture, the alkyl in described alkylbenzenesulfonate is preferably C14~C22Alkyl；Described cationic surfactant preferably has
One C10~C22Alkyl and three C1～C4Alkyl is connected with described nitrogen-atoms, more preferably has a C10~C22Alkyl and three
Methyl is connected with described nitrogen-atoms, or more preferably has a C10~C22Alkyl and three ethyls are connected with described nitrogen-atoms.
The viscosity-average molecular weight of described modified polyacrylamide is preferably 500 ~ 9,000,000；Described compound oil displacement agent, in terms of mass fraction, excellent
Choosing includes negative and positive system surfactant 0.03～0.6 part；Described compound oil displacement agent, in terms of mass fraction, preferably includes polymerization
Thing 0.05～0.2 part.
Described water can be that (such as KCl, NaCl, inorganic salt is water-soluble at inorganic salt for the water after deionized water, interpolation inorganic salt
Content preferably 1 ~ 15wt% in liquid), water containing mineral, wherein the water containing mineral can be tap water, river, oil field stratum
Water, all can reach the purpose of the present invention, but consider from environmental conservation and economic factor, preferably oil field stratum water；Oil field stratum
The total salinity of water is preferably 5000～15000 mg/litre, and further preferably water type is NaHCO3Type.
The oil displacement agent used in flooding method of the present invention can also be containing polymer (such as polyacrylamide commonly used in the art
Amine etc.), foam, small organic molecule (such as DMSO etc.), solid or liquid base be (such as sodium hydroxide, sodium carbonate, bicarbonate
Sodium, diethanolamine or triethanolamine) etc. oil recovery auxiliary agent.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: use one of above-mentioned technical problem
The flooding method of described compound oil displacement agent, by described compound oil displacement agent in displacement of reservoir oil temperature 40 ~ 100 DEG C, total salinity > 1000 millis
Contact with oil bearing bed under grams per liter oil field stratum water condition, by the mother oil displacement in described oil bearing bed out.
In technique scheme, described displacement of reservoir oil temperature is preferably 60～90 DEG C；The total salinity of oil field stratum water is preferred
1000～15000 mg/litre, more preferably total salinity are 5000～15000 mg/litre；The water type of oil field stratum water is preferred
NaHCO3Type.
Flooding method of the present invention, it is also possible to include water drive commonly used in the art, polymer flooding, poly-table alkali ternary composite driving,
Steam drives and foam flooding etc..
In technique scheme, described compound oil displacement agent can use various conventional method to mix according to each component of aequum
For the displacement of reservoir oil after uniformly；But within the easier short time, obtain uniform oil displacement agent meter, combination flooding described in technique scheme
The preparation of oil preparation preferably includes following steps:
(1) the desired amount of anion surfactant, cationic surfactant, water and low-carbon alcohols are added mixing container
In, wherein low-carbon alcohols accounts for the 5～70wt% of water and low-carbon alcohols gross weight by weight；
(2) it is warming up to 40 ~ 100 DEG C stir 1～4 hour；
(3) boil off low-carbon alcohols, obtain negative and positive system surfactant solution；
(4) negative and positive system surfactant solution step 3) obtained and the desired amount of polymer mix with water, stir
Mix 1～4 hour.
Described low-carbon alcohols is selected from C1~C5Fatty alcohol, preferably preferably be selected from methanol, ethanol, normal propyl alcohol or isopropanol.
The inventive method uses physical modeling's displacement evaluation methodology to carry out effect assessment, and concrete evaluation methodology is:
By rock core constant temperature drying to constant weight, measure the perm-plug method of rock core；With above-mentioned output water saturation rock core, calculate it
Pore volume, at a temperature of the displacement of reservoir oil, with crude oil saturated core, records the volume of saturated crude oil, pumps into the speed of 0.2ml/min
Oil field stratum water, is driven to aqueous reach 99%, calculates water drive and improve the recovery ratio of crude oil, then with the speed tuberculosis of 0.2ml/min
After 0.1 ~ 1PV (rock pore volume) compound oil displacement agent, with the speed water drive extremely aqueous 100% of 0.2ml/min, calculate in water drive
On the basis of improve the percent of oil recovery factor.
In technique scheme, described modified polyacrylamide is by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid
Two kinds of monomer copolymerizations form, and can buy from market, it is also possible to prepared by conventional water solution polymerization process.No matter block copolymerization
Or random copolymerization, the product obtained is used equally to the present invention and reaches the purpose of the present invention.Modification in the embodiment of the present invention
Polyacrylamide, is according to mol ratio (1 ~ 4) by acrylamide and two kinds of monomers of 2-acrylamide-2-methylpro panesulfonic acid: 1 mixes
Raolical polymerizable is caused to obtain with water for solvent conventional radical initiators after conjunction.
The negative and positive system surfactant that anion prepared by the present invention and cationic surfactant are formed, due to the moon from
After son is compounding with cationic surfactant, the increase of surface activity, the decline of critical micelle concentration, solubilising effect can be presented
Advantage should be waited.This is because the hydrophilic head base in anion surfactant be elecrtonegativity with ammonium in cationic surfactant from
There is strong electrostatic interaction in sub-positive charge, promotes two kinds of band interionic associations of difference charged surfactant, and the two
The hydrocarbon interchain of hydrophobic group also have certain hydrophobic interaction, promote different surfaces active agent molecule to take the more side of being closely spaced
Formula, thus it is readily formed micelle in the solution, produce surface activity more higher than single surfactant and low critical glue
Bundle concentration.Two surfactants in negative and positive system surfactant are ion-type, and built agent also shows ion surface
The feature of activating agent, the most excellent heat resistance.Therefore, this surfactant had both had excellent heat-resisting property, had again excellent
Different interfacial activity, it is possible to resolve the interfacial tension that Oil Field causes because surfactant concentration progressively declines during using
Rising problem so that surfactant, in the migration process of down-hole, still can keep ultralow oil-water interfaces to open even if concentration is relatively low
Power such that it is able to improve oil displacement efficiency.Further, since formation core surface presents the characteristic of mixing moistening more, contain the most simultaneously
Glossy wet structure and water-wet surface, negative and positive system surfactant can effectively change the wettability of rock layer surface, particularly
Cationic surfactant by with absorption electronegative Interaction of substituents on a solid surface, glossy wet structure can be made to change
Become neutral wetting or water-wet surface, reduce the crude oil adhesion work at the surface of solids so that crude oil is easily peeled off, and improves and washes
The raising of oil efficiency, beneficially oil recovery factor.
In the embodiment of the present invention, the concentration of the negative and positive system surfactant related to when testing, all with test fluid
In containing anion and the total amount meter of cationic surfactant component in technique scheme.
Use the polymer of the present invention and negative and positive system surfactant compound oil displacement agent and flooding method, in alkali-free condition
Under, can be used for formation temperature 60 ~ 90 DEG C, the NaHCO of salinity 5000～20000 mg/litre3The husky 7 block ground of type Jiangsu oilfield
Layer water and crude oil, by percentage to the quality, consumption is 0.03～0.6wt% negative and positive system surfactant and 0.05～0.2wt%
Above-mentioned modified polyacrylamide forms oil displacement agent compositions, determines the apparent viscosity of this oil displacement agent composition solution, with
Dynamical interfacial tension value between the husky 7 block dewatered oils of Jiangsu oilfield is up to 10-2～10-4MN/m low interfacial tension, through physics
Simulation displacement experiment Lab-evaluation, this oil displacement agent can improve oil recovery factor on the basis of water drive up to 13.76%, achieve relatively
Good technique effect.
Accompanying drawing explanation
Fig. 1 is simulation core displacement experiment flow chart.
In Fig. 1,1 is constant-flux pump, and 2 is six-way valve, and 3 is intermediate receptacle, and 4 is pharmacy jar, and 5 is compression pump, and 6 is six-way valve, 7
For fill out sand tube, 8 is graduated cylinder.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
(1) octadecyl benzenesulfonic acid sodium is added in reaction bulb with tetradecyl trimethyl ammonium chloride 5:1 in molar ratio, with
40wt% ethanol water is solvent, be warming up to 70 DEG C stirring 2.5 hours to being completely dissolved, decompression distillation remove ethanol, obtain institute
The negative and positive system surfactant needed, wherein surfactant total content is 45.1% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 15000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=600 ten thousand) aqueous solution, stir 3 hours, then both is mixed to get a kind of uniform
Poly-table compound oil displacement agent, measures viscosity and the oil water interfacial tension of 7 dewatered oils husky with Jiangsu oilfield of system, and test temperature is
83 DEG C, it is shown in Table 1.Apparent viscosity is by the BROODFIELD of Brookfield company of the U.S.I type viscometer measures, and interface is opened
The TX500 type that power is produced by Texas ,Usa university rotates and drips interfacial tensimeter mensuration.
(3) by shale artificial core constant temperature drying to constant weight, measure average diameter and the rock core length of rock core, weigh rock core
Dry weight, measures the perm-plug method of rock core.With above-mentioned formation water saturated core, test its pore volume.Former with husky 7 block dehydrations
Oil saturated core, records the volume of saturated crude oil.At a temperature of 83 DEG C, it is driven to husky 7 formation waters that Produced Liquid is aqueous reaches 99%, meter
Calculate water drive and improve the recovery ratio of crude oil, the Surfactant/Polymer that tuberculosis 0.3pv (rock pore volume) step (2) synthesizes
After binary composite oil displacement agent, water drive to aqueous 100%, calculates the percent improving oil recovery factor on the basis of water drive, simultaneously with
Note the polymer phase contrast of identical PV, be shown in Table 1.Rock core perm-plug method HKGP-3 type compact rock core gas permeability hole
Porosity analyzer measures, and the simulation core displacement experiment flow process of employing is as shown in Figure 1.
Table 1
| Oil displacement system | 0.3wt%S1 | 0.1wt%P1 | 0.3%wtS1+0.1wt%P1 |
| Oil water interfacial tension/mN.m-1 | 6.32×10-4 | / | 1.51×10-3 |
| Viscosity/mPa s | / | 3.51 | 4.13 |
| Improve recovery ratio/% | / | 9.18 | 14.76 |
Note: in table 1, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S1 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 2]
(1) petroleum sodium sulfonate is added in reaction bulb with Tetradecyl Trimethyl Ammonium Bromide 8:1 in molar ratio, with 20wt%
Methanol aqueous solution is solvent, be warming up to 50 DEG C stirring 3 hours to being completely dissolved, decompression distillation remove methanol, obtain required the moon
Sun system surfactant, wherein surfactant total content is 45.3% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 20000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=900 ten thousand) aqueous solution, stir 4 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 2.
(3) employing 75 DEG C is as displacement of reservoir oil temperature, and remaining, with [embodiment 1] (3), the results are shown in Table shown in 2.
Table 2
| Oil displacement system | 0.3wt%S2 | 0.07wt%P2 | 0.3%wtS1+0.07wt%P1 |
| Oil water interfacial tension/mN.m-1 | 1.32×10-3 | / | 3.66×10-3 |
| Viscosity/mPa s | / | 3.22 | 3.67 |
| Improve recovery ratio/% | / | 9.01 | 12.86 |
Note: in table 2, P2 is modified polyacrylamide (AM/AMPS mol ratio=4:1, M=900 ten thousand)；S2 is step (1) system
Standby negative and positive system surfactant.
[embodiment 3]
(1) by alpha-olefin sodium sulfonate (for commercially available C16~C18Alpha-olefin azochlorosulfonate acid sodium mixture) and trimethyl chlorine
Change ammonium 10:1 in molar ratio and add in reaction bulb, with 30wt% isopropanol water solution as solvent, be warming up to 60 DEG C and stir 3 hours extremely
Being completely dissolved, isopropanol is removed in decompression distillation, obtains required negative and positive system surfactant, wherein surfactant total content
It is 50.9% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 10000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=600 ten thousand) aqueous solution, stir 2 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 3.
(3) employing 90 DEG C is as displacement of reservoir oil temperature, injects 0.2PV, and remaining, with [embodiment 1] (3), the results are shown in Table shown in 3.
Table 3
| Oil displacement system | 0.05wt%S3 | 0.2wt%P1 | 0.05wt%S3+0.2wt%P1 |
| Oil water interfacial tension/mN.m-1 | 4.32×10-4 | / | 7.80×10-4 |
| Viscosity/mPa s | / | 5.12 | 5.28 |
| Improve recovery ratio/% | / | 11.21 | 13.97 |
Note: in table 3, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S3 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 4]
(1) sodium lignin sulfonate is added in reaction bulb with octadecyl trimethyl ammonium chloride 1.2:1 in molar ratio, with
50wt% normal propyl alcohol aqueous solution is solvent, be warming up to 90 DEG C stirring 1.5 hours to being completely dissolved, decompression distillation remove normal propyl alcohol,
To required negative and positive system surfactant, wherein surfactant total content is 42.5% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 10000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=700 ten thousand) aqueous solution, stir 3 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 4.
(3) employing 85 DEG C is as displacement of reservoir oil temperature, and remaining, with [embodiment 1] (3), the results are shown in Table shown in 4.
Table 4
| Oil displacement system | 0.2wt%S4 | 0.1wt%P3 | 0.2wt%S1+0.1wt%P3 |
| Oil water interfacial tension/mN.m-1 | 3.32×10-4 | / | 5.69×10-4 |
| Viscosity/mPa s | / | 3.82 | 4.57 |
| Improve recovery ratio/% | / | 9.22 | 13.98 |
Note: in table 4, P3 is modified polyacrylamide (AM/AMPS mol ratio=2.5:1, M=700 ten thousand)；S4 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 5]
(1) sodium laurate is added in reaction bulb with Dodecyl trimethyl ammonium chloride 15:1 in molar ratio, with 10wt%
Isopropanol water solution is solvent, is warming up to 80 DEG C of stirrings 2 hours to being completely dissolved, and isopropanol is removed in decompression distillation, obtains required
Negative and positive system surfactant, wherein surfactant total content is 40.8% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 5000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=600 ten thousand) aqueous solution, stir 2 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 5.
(3) injecting 0.2PV, remaining, with [embodiment 1] (3), the results are shown in Table shown in 5.
Table 5
| Oil displacement system | 0.1wt%S5 | 0.1wt%P1 | 0.1wt%S5+0.1wt%P1 |
| Oil water interfacial tension/mN.m-1 | 3.45×10-3 | / | 5.11×10-3 |
| Viscosity/mPa s | / | 3.52 | 4.69 |
| Improve recovery ratio/% | / | 9.18 | 13.74 |
Note: in table 5, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S5 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 6]
(1) myristyl benzene sulfonic acid sodium salt is added reaction bulb with INCROQUAT TMC-80 ECONOL TM22 1.5:1 in molar ratio
In, with 10wt% isopropanol water solution as solvent, be warming up to 80 DEG C stirring 2 hours to being completely dissolved, decompression distillation remove isopropyl
Alcohol, obtains required negative and positive system surfactant, and wherein surfactant total content is 45.6% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 15000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=700 ten thousand) aqueous solution, stir 3 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 6.
(3) employing 65 DEG C is as displacement of reservoir oil temperature, injects 0.4PV, and remaining, with [embodiment 1] (3), the results are shown in Table shown in 6.
Table 6
| Oil displacement system | 0.3wt%S6 | 0.1wt%P3 | 0.3%wtS6+0.1wt%P3 |
| Oil water interfacial tension/mN.m-1 | 7.98×10-4 | / | 1.08×10-3 |
| Viscosity/mPa s | / | 3.82 | 5.11 |
| Improve recovery ratio/% | / | 9.24 | 13.96 |
Note: in table 6, P3 is modified polyacrylamide (AM/AMPS mol ratio=2.5:1, M=700 ten thousand)；S6 is step (1) system
Standby negative and positive system surfactant.
[embodiment 7]
(1) by alpha-olefin sodium sulfonate (for commercially available C14～C16 Alpha-olefin azochlorosulfonate acid sodium mixture) and tetradecyltrimethylammonium chlorine
Change ammonium 20:1 in molar ratio and add in reaction bulb, with 40wt% ethanol water as solvent, be warming up to 70 DEG C and stir 3 hours to the completeest
CL, decompression distillation removal ethanol, obtain required negative and positive system surfactant, wherein surfactant total content is with matter
Amount percentages is 42.3%.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 10000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=600 ten thousand) aqueous solution, stir 2 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 7.
(3) employing 85 DEG C is as displacement of reservoir oil temperature, injects 0.1PV, and remaining, with [embodiment 1] (3), the results are shown in Table shown in 7.
Table 7
| Oil displacement system | 0.05wt%S7 | 0.2wt%P1 | 0.05wt%S7+0.2%P1 |
| Oil water interfacial tension/mN.m-1 | 5.32×10-3 | / | 6.43×10-3 |
| Viscosity/mPa s | / | 5.12 | 5.36 |
| Improve recovery ratio/% | / | 11.21 | 13.55 |
Note: in table 7, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S7 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 8]
(1) enuatrol is added in reaction bulb with Tetradecyl Trimethyl Ammonium Bromide 12:1 in molar ratio, with 20wt% just
Aqueous propanol solution is solvent, be warming up to 60 DEG C stirring 3 hours to being completely dissolved, decompression distillation remove normal propyl alcohol, obtain required
Negative and positive system surfactant, wherein surfactant total content is 43.5% by percentage to the quality.
(2) with Jiangsu oilfield husky 7 formation waters (TDS 20000mg/L) the negative and positive diagram of system that respectively prepared by preparation steps (1)
Face activating agent and modified polyacrylamide (M=900 ten thousand) aqueous solution, stir 4 hours, and remaining, with [embodiment 1] (2), the results are shown in Table
Shown in 8.
(3) with [embodiment 1] (3), the results are shown in Table shown in 8.
Table 8
| Oil displacement system | 0.2wt%S8 | 0.1wt%P2 | 0.2wt%S8+0.1wt%P2 |
| Oil water interfacial tension/mN.m-1 | 1.32×10-3 | / | 3.66×10-3 |
| Viscosity/mPa s | / | 4.64 | 5.55 |
| Improve recovery ratio/% | / | 10.53 | 14.26 |
Note: in table 8, P2 is modified polyacrylamide (AM/AMPS mol ratio=4:1, M=900 ten thousand)；S8 is step (1) system
Standby negative and positive system surfactant.
[embodiment 9]
Except by " mol ratio of octadecyl benzenesulfonic acid sodium and tetradecyl trimethyl ammonium chloride changes 1.05:1 into ", remaining
With [embodiment 1], the results are shown in Table shown in 9.
Table 9
| Oil displacement system | 0.3wt%S9 | 0.1wt%P1 | 0.3%wtS9+0.1wt%P1 |
| Oil water interfacial tension/mN.m-1 | 4.32×10-3 | / | 4.11×10-3 |
| Viscosity/mPa s | / | 3.51 | 3.69 |
| Improve recovery ratio/% | / | 9.18 | 11.91 |
Note: in table 9, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S9 is step (1)
The negative and positive system surfactant of preparation.
[embodiment 10]
Except by " octadecyl benzenesulfonic acid sodium changes 30:1 into the mol ratio of tetradecyl trimethyl ammonium chloride ", remaining is same
[embodiment 1], the results are shown in Table shown in 10.
Table 10
| Oil displacement system | 0.3wt%S10 | 0.1wt%P1 | 0.3%wtS10+0.1wt%P1 |
| Oil water interfacial tension/mN.m-1 | 1.25×10-2 | / | 2.36×10-2 |
| Viscosity/mPa s | / | 3.51 | 3.96 |
| Improve recovery ratio/% | / | 9.18 | 11.89 |
Note: in table 10, P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S10 is step
(1) the negative and positive system surfactant prepared.
From embodiment 1 to embodiment 10 it can be seen that rubbing at anion surfactant and cationic surfactant
You are than being all can to reach the purpose of the present invention in the range of 1 ~ 100: 1, but have superior technique in the range of 1.2 ~ 20:1
Effect.
[comparative example 1]
Except with " polyacrylamide (M=600 ten thousand) " replacement " modified polyacrylamide P1(AM/AMPS mol ratio=1.5:1
, M=600 ten thousand) ", remaining, with [embodiment 1], the results are shown in Table shown in 11.
Table 11
| Oil displacement system | 0.3wt%S1 | 0.1wt%P4 | 0.3%wtS1+0.1wt%P4 |
| Oil water interfacial tension/mN.m-1 | 3.25×10-2 | / | 5.36×10-2 |
| Viscosity/mPa s | / | 3.05 | 3.16 |
| Improve recovery ratio/% | / | 6.11 | 9.87 |
Note: P4 is polyacrylamide (M=600 ten thousand)；S1 is negative and positive system surfactant prepared by step (1).
[comparative example 2]
Except with " polyacrylamide (M=900 ten thousand) " replacement " modified polyacrylamide P2(AM/AMPS mol ratio=4:1, M
=900 ten thousand) ", remaining, with [embodiment 2], the results are shown in Table shown in 12.
Table 12
| Oil displacement system | 0.3wt%S2 | 0.07wt%P5 | 0.3%wtS1+0.07wt%P5 |
| Oil water interfacial tension/mN.m-1 | 1.32×10-3 | / | 3.66×10-3 |
| Viscosity/mPa s | / | 3.11 | 3.27 |
| Improve recovery ratio/% | / | 6.32 | 9.60 |
Note: P5 is polyacrylamide (M=900 ten thousand)；S2 is negative and positive system surfactant prepared by step (1).
[comparative example 3]
Except with " octadecyl benzenesulfonic acid sodium " replacement " octadecyl benzenesulfonic acid sodium and tetradecyl trimethyl ammonium chloride
The negative and positive system surfactant formed ", remaining, with [embodiment 1], the results are shown in Table shown in 13.
Table 13
| Oil displacement system | 0.3wt%S11 | 0.1wt%P1 | 0.3%wtS11+0.1wt%P1 |
| Oil water interfacial tension/mN.m-1 | 7.19×10-2 | / | 7.67×10-2 |
| Viscosity/mPa s | / | 3.51 | 3.82 |
| Improve recovery ratio/% | / | 9.18 | 10.76 |
Note: P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S11 is octadecyl benzene sulphur
Acid sodium.
[comparative example 4]
Except so that " alpha-olefin sodium sulfonate is (for commercially available C16~C18 Alpha-olefin azochlorosulfonate acid sodium mixture) " replacement " alpha-olefin sulfonic acid
Sodium is (for commercially available C16~18 Alpha-olefin azochlorosulfonate acid sodium mixture) and the negative and positive system surface activity of Dodecyl trimethyl ammonium chloride formation
Agent ", remaining, with [embodiment 3], the results are shown in Table shown in 14.
Table 14
| Oil displacement system | 0.05wt%S12 | 0.2wt%P1 | 0.05wt%S12+0.2wt%P1 |
| Oil water interfacial tension/mN.m-1 | 7.98×10-2 | / | 1.02.×10-1 |
| Viscosity/mPa s | / | 5.12 | 5.14 |
| Improve recovery ratio/% | / | 11.21 | 11.84 |
Note: P1 is modified polyacrylamide (AM/AMPS mol ratio=1.5:1, M=600 ten thousand)；S12 is alpha-olefin sulfonic acid
Sodium (C16~18).
Claims (10)
1. containing polymer and the compound oil displacement agent of negative and positive system surfactant, in terms of mass fraction, including following components:
The negative and positive system surfactant of (1) 0.01～5.0 part；
The polymer of (2) 0.01～3.0 parts；
The water of (3) 90.0～99.9 parts；
Described negative and positive system surfactant by anion surfactant and quaternary ammonium cation surfactant with mol ratio 1
～100:1 composition；Described anion surfactant is any one in sulfonate, carboxylate or phosphate, in structure
Lipophilic group is C8～C30Alkyl；Described cationic surfactant has C8～C30Alkyl and described cationic surfactant
Nitrogen-atoms in structure is connected, and described cationic surfactant is quaternary ammonium salt；Described polymer is modified polyacrylamide, by
Acrylamide, two kinds of monomer copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid form, two kinds of monomer lists in modified polyacrylamide
The mol ratio of unit is 1～4: 1, and viscosity-average molecular weight is 300～10,000,000；
Described compound oil displacement agent does not contains alkali.
Compound oil displacement agent the most according to claim 1, it is characterised in that described negative and positive system surfactant is by anion
Surfactant forms with mol ratio 1.2～20:1 with cationic surfactant.
Compound oil displacement agent the most according to claim 1, it is characterised in that described anion surfactant is benzene sulfonamide
Hydrochlorate, C12～C22Alpha-alkene sulfonate, C9～C17Appointing in carboxylate, mahogany acid, petroleum carboxylate or lignosulfonates
Meaning one or mixture, the alkyl in described alkylbenzenesulfonate is C14～C22Alkyl；Described cationic surfactant has
One C10～C22Alkyl and three C1～C4Alkyl is connected with described nitrogen-atoms.
Compound oil displacement agent the most according to claim 3, it is characterised in that described cationic surfactant has a C10
～C22Alkyl and three methyl are connected with described nitrogen-atoms, or have a C10～C22Alkyl and three ethyls and described nitrogen
Atom is connected.
Compound oil displacement agent the most according to claim 1, it is characterised in that the viscosity-average molecular weight of described modified polyacrylamide
It is 500～9,000,000.
Compound oil displacement agent the most according to claim 1, it is characterised in that described compound oil displacement agent, in terms of mass fraction, bag
Include negative and positive system surfactant 0.03～0.6 part.
Compound oil displacement agent the most according to claim 1, it is characterised in that described compound oil displacement agent, in terms of mass fraction, bag
Include polymer 0.05～0.2 part.
8. use the flooding method according to compound oil displacement agent according to any one of claim 1 to 7, described compound oil displacement agent is existed
Displacement of reservoir oil temperature 40～100 DEG C, total salinity > contact with oil bearing bed under 1000 mg/litre oil field stratum water conditions, contain described
Mother oil displacement in oil formation is out.
Flooding method the most according to claim 8, it is characterised in that described displacement of reservoir oil temperature is 60～90 DEG C.
Flooding method the most according to claim 8, it is characterised in that described oil field stratum water, total salinity be 5000～
15000 mg/litre.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310044451.0A CN103965852B (en) | 2013-02-05 | 2013-02-05 | Containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method |
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| CN201310044451.0A CN103965852B (en) | 2013-02-05 | 2013-02-05 | Containing polymer and the compound oil displacement agent of negative and positive system surfactant and flooding method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN106634931A (en) * | 2017-01-19 | 2017-05-10 | 中国科学院理化技术研究所 | Foam oil displacement agent with anti-adsorption performance and application thereof |
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