CN116004213B - Surfactant/nanoparticle composite oil displacement agent and preparation method and application thereof - Google Patents
Surfactant/nanoparticle composite oil displacement agent and preparation method and application thereof Download PDFInfo
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- CN116004213B CN116004213B CN202111230154.6A CN202111230154A CN116004213B CN 116004213 B CN116004213 B CN 116004213B CN 202111230154 A CN202111230154 A CN 202111230154A CN 116004213 B CN116004213 B CN 116004213B
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 80
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 55
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920000570 polyether Polymers 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 79
- 239000002245 particle Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 25
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- -1 polysiloxane Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 11
- 229960003237 betaine Drugs 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- HSEMFIZWXHQJAE-UHFFFAOYSA-N Amide-Hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- MWYMHZINPCTWSB-UHFFFAOYSA-N dimethylsilyloxy-dimethyl-trimethylsilyloxysilane Chemical class C[SiH](C)O[Si](C)(C)O[Si](C)(C)C MWYMHZINPCTWSB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 6
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical class C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229940117986 sulfobetaine Drugs 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- BQYPERTZJDZBIR-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical class C[SiH]1O[SiH](C)O[SiH](C)O[SiH](C)O1 BQYPERTZJDZBIR-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- ZFJFYUXFKXTXGT-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilane Chemical class C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C ZFJFYUXFKXTXGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000033558 biomineral tissue development Effects 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 2
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- JHKBMYNOLVYFHD-UHFFFAOYSA-N trimethyl(trimethylsilyloxysilyloxy)silane Chemical class C[Si](C)(C)O[SiH2]O[Si](C)(C)C JHKBMYNOLVYFHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010779 crude oil Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011435 rock Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OOFAEFCMEHZNGP-UHFFFAOYSA-N 1-n',1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(N)N(C)C OOFAEFCMEHZNGP-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- SQXSZTQNKBBYPM-UHFFFAOYSA-N 2-[docosyl(dimethyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O SQXSZTQNKBBYPM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- PFIOPNYSBSJFJJ-UHFFFAOYSA-M sodium;2-octylbenzenesulfonate Chemical compound [Na+].CCCCCCCCC1=CC=CC=C1S([O-])(=O)=O PFIOPNYSBSJFJJ-UHFFFAOYSA-M 0.000 description 1
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 1
- AEINUXRPXXDADS-UHFFFAOYSA-N sodium;tetradecan-1-ol Chemical compound [Na].CCCCCCCCCCCCCCO AEINUXRPXXDADS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a surfactant/nanoparticle composite oil displacement agent, and a preparation method and application thereof. The surfactant/nanoparticle composite oil displacement agent provided by the invention comprises a zwitterionic surfactant, an anionic surfactant, polyether organosilicon modified silica particles and water. The preparation method provided by the invention comprises the steps of dissolving components comprising the surfactant in water, adding polyether organosilicon modified silica particles into the aqueous solution of the surfactant, and uniformly dispersing to obtain the composite oil displacement agent. The compound oil displacement agent does not contain alkali, has high oil displacement efficiency, and can be used as an alkali-free oil displacement agent in the enhanced oil recovery production of oil fields.
Description
Technical Field
The invention belongs to the technical field of oilfield chemistry, and particularly relates to a surfactant/nanoparticle composite oil displacement agent, and a preparation method and application thereof.
Background
The surfactant has the functions of reducing interfacial tension, wetting inversion, oil-water emulsification, solubilization, improving surface charge density and the like, and has important application in improving recovery efficiency of oil fields.
At present, the interfacial tension between crude oil and water under the alkali-free condition often cannot meet the requirements and the oil displacement effect is affected by petroleum sulfonate, heavy alkylbenzene sulfonate, natural carboxylate, petroleum carboxylate and the like which are commonly used in tertiary oil recovery.
Patent CN 1439689a reports a ternary complex oil displacement system consisting of two anionic surfactants, ethylene glycol, isopropanol, polymer and base; patent CN 1394935A discloses a chemical agent, which mainly comprises sodium octylbenzenesulfonate surfactant, surfactant auxiliary agent, surfactant synergist and surfactant solubilizer, and can reduce oil-water interfacial tension and raise oil washing efficiency. The surfactant has the problems that the displacement fluid system is added with alkali, alkaline salt or alcohol and other surface active aids, so that the displacement fluid is too complex, produced fluid is difficult to demulsifie, and meanwhile, the stratum and equipment are damaged.
Patent CN 86107891a reports a surfactant flooding system which does not add alcohol and auxiliary agent, has low interfacial tension and higher solubilization parameter, however the application concentration of the surfactant of the system is high and is not lower than 0.5%.
Nanoparticles are receiving increasing attention in the petroleum industry due to their unique small size and surface effects. Patent CN 1818008a discloses an oil displacement agent which is prepared from petroleum sulfonate and modified silicon dioxide, and can reduce the oil-water interfacial tension, but petroleum sulfonate products have complex composition, polydisperse molecular weight, difficult quality control and poor performance stability.
Disclosure of Invention
The invention provides a novel surfactant/nanoparticle composite oil displacement agent, which aims to solve the problems of poor oil displacement efficiency, high use concentration, corrosion and scale damage to stratum and oil well caused by alkali contained in an oil displacement system and difficult demulsification in the tertiary oil recovery process in the prior art.
The invention aims to provide a surfactant/nanoparticle composite oil displacement agent, which comprises a surfactant, nanoparticles and water, wherein the surfactant comprises a zwitterionic surfactant and an anionic surfactant, and the nanoparticles are polyether organosilicon modified silica particles.
Preferably, the method comprises the steps of,
The particle size of the nano particles is 10-300 nm, preferably 30-200 nm;
In the compound oil displacement agent, the mass ratio of the amphoteric ion surfactant to the anionic surfactant to the nano particles is 1: (0.01-100): (0.01 to 100), preferably 1: (0.1-10): (0.4-2);
The total concentration of the surfactant and the nano particles in the compound oil displacement agent is 0.01-1%, preferably 0.01-0.5% by mass percent;
the mineralization degree of the water is 0-50000 mg/L based on the weight of NaCl;
the structure of the amphoteric ion surfactant is as follows:
Wherein R 1 is a hydrocarbon group of C 6～C32 or a group of the structure R 1-CO-NH-R2 -, wherein R 1 is selected from hydrocarbon groups of C 6～C32 and R 2 is selected from alkylene groups of C 1～C10; r 2、R3 is independently selected from hydrocarbyl or substituted hydrocarbyl of C 1～C5, R 4 is selected from alkylene or hydroxy substituted alkylene of C 1～C4; x is selected from SO 3 - or COO -; preferably, the zwitterionic surfactant is at least one selected from dodecyl betaine, cetyl amide carboxyl betaine, cetyl sulfo betaine, oleic amide carboxyl betaine, erucic amide carboxyl betaine and behenyl betaine, preferably at least one selected from cetyl amide carboxyl betaine, oleic amide carboxyl betaine and cetyl sulfo betaine;
The structural formula of the anionic surfactant is at least one of the formula (1) and the formula (2):
R 5 -YM type (1)
R 5-O-(R7-O)n-R6 -YM (2)
Wherein R 5 is selected from the hydrocarbon group of C 6～C20; r 6 is selected from alkylene or hydroxy-substituted alkylene of C 1～C4; y is selected from SO 3 - or COO -, and M is selected from a cation or a cationic group; r 7 is selected from the straight chain or branched chain alkylene of C 2～C4, n is selected from the integer of 1-30; preferably, the anionic surfactant is at least one selected from alpha-olefin sodium sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium tetradecyl polyoxyethylene ether carboxylate, sodium stearyl polyoxyethylene ether hydroxypropyl sulfonate and sodium stearyl benzene sulfonate, preferably at least one selected from sodium stearyl polyoxyethylene ether hydroxypropyl sulfonate, sodium tetradecyl polyoxyethylene ether carboxylate and sodium dodecyl benzene sulfonate;
The nano particles are obtained by modifying silicon dioxide particles by components comprising polyether modified polysiloxane and a silane coupling agent, wherein the silane coupling agent is selected from a chloralkyl silane coupling agent, preferably at least one of 3-chloropropyl trimethoxy silane and 3-chloropropyl triethoxy silane; the polyether modified polysiloxane is at least one selected from polyether modified hexamethyltrisiloxane, polyether modified heptamethyltrisiloxane, polyether modified tetramethyl cyclotetrasiloxane, polyether modified octamethyltetrasiloxane, polyether modified decamethyl pentasiloxane and polyether modified hydrogen-containing silicone oil, and preferably at least one selected from polyether modified heptamethyltrisiloxane and polyether modified octamethyltetrasiloxane.
The second object of the invention is to provide a preparation method of the surfactant/nanoparticle composite oil displacement agent, which comprises the steps of dissolving components including the amphoteric surfactant and the anionic surfactant in water, adding the polyether organosilicon modified silica particles into the aqueous solution of the surfactant, and uniformly dispersing to obtain the surfactant/nanoparticle composite oil displacement agent.
The preparation method of the polyether organosilicon modified silicon dioxide particles specifically comprises the following steps:
Step a, dispersing nano silicon dioxide particles in a solvent S 1, adding a silane coupling agent, heating and stirring for reaction to obtain coupling agent modified silicon dioxide particles;
And b, dispersing the coupling agent modified silicon dioxide particles obtained in the step a in a solvent S 2, adding polyether modified polysiloxane, and heating and stirring to react to obtain the polyether organosilicon modified silicon dioxide particles.
The preparation method of the polyether organosilicon modified silica particles comprises the following steps:
the particle size of the nano silicon dioxide particles is 10-300 nm, preferably 30-200 nm;
the solvent S 1 is selected from organic solvents, preferably selected from one of toluene, xylene and ethanol;
the solvent S 2 is selected from an organic solvent, preferably at least one selected from N, N-dimethylformamide, acetonitrile and toluene;
In the step a, the mass ratio of the nano silicon dioxide particles to the silane coupling agent to the solvent S 1 is (2-15): (2-23): 100, preferably (5 to 10): (5-12): 100;
in the step b, the mass ratio of the coupling agent modified silicon dioxide to the polyether modified polysiloxane to the solvent S 2 is (2-15): (5-60): 100, preferably (5 to 10): (10-38): 100;
The reaction temperature in the step a is 60-150 ℃ and the reaction time is 4-30 h; preferably, the reaction time is 80-120 ℃ and the reaction time is 6-20 h; the reaction temperature in the step b is 60-150 ℃ and the reaction time is 8-30 h; preferably, the reaction time is 80-120 ℃ and 16-24 hours;
In step b, an alkaline compound is also required to be added; wherein the alkaline compound is selected from inorganic alkaline compounds, preferably at least one of sodium hydroxide and potassium hydroxide; the mass ratio of the added alkaline compound to the solvent S 2 is (0.3-4): 100, preferably (0.8 to 2.6): 100;
The solid obtained by the reaction in the steps a-b is also required to be washed and dried, wherein the washing can be realized by adopting a washing mode commonly used in the field, and the adopted solvent is at least one of methanol, ethanol, toluene and acetone, preferably at least one of ethanol and toluene; the drying is carried out by adopting common drying equipment, preferably, the drying temperature is 20-100 ℃, and preferably 40-80 ℃.
The nano silicon dioxide adopted in the preparation method can be commercially available products, and can also be prepared by the following method: adding silicate compound into alkaline solution, stirring, reacting, washing, drying to obtain nano silicon dioxide particles, wherein the silicate compound is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; the alkaline compound in the alkaline solution is selected from ammonia water, and the solvent in the alkaline solution is selected from alcohol solvents, preferably at least one selected from methanol, ethanol, isopropanol and n-butanol; the volume ratio of the silicate compound to the alkaline compound to the solvent is (1-15): (2-20): 100, preferably (3 to 10): (4-12): 100; the reaction temperature is 10-60 ℃ and the reaction time is 2-48 h; preferably, the reaction time is 20-45 ℃ and the reaction time is 6-24 h.
Due to the existence of the nano particles, the structure partial pressure exists in the wedge-shaped area of the oil-rock two-phase contact, and the pressure is far greater than the van der Waals force, the electrostatic force and the like among the particles, so that the displacement fluid is promoted to flow, enter the oil-rock two-phase contact surface, expand on the rock surface, replace the original interface film and realize the separation of oil and rock. It spreads more easily over the rock surface than a displacement fluid without particles, effectively stripping crude oil. In addition, the nano particles and the surfactant are mutually complemented and adsorbed on the oil-water interface, so that a compact interfacial film with mechanical strength can be formed, and the activated residual oil can be transported in the stratum for a long time so as to be extracted.
The invention further aims to provide the surfactant/nanoparticle composite oil displacement agent or application of the surfactant/nanoparticle composite oil displacement agent obtained by the preparation method in tertiary oil recovery.
In the above technical solution, the specific method of application may be to inject the oil displacement agent into the oil reservoir stratum to contact with the underground crude oil, so as to displace the underground crude oil. The invention combines the advantages of polyether modified polysiloxane and nano silicon dioxide particles to prepare modified nano particles, and combines the modified nano particles with the amphoteric ion surfactant and the anionic surfactant to form a composite flooding, so that the interfacial activity of the system can be obviously improved, and the modified nano particles are used for tertiary oil recovery. In the composite flooding adopted by the invention, polyether organosilicon modified silicon dioxide particles can promote the flow of a displacement fluid and replace an original interfacial film, so that the separation of crude oil and rock is realized, after crude oil is stripped, nano particles and a surfactant are mutually complemented and adsorbed on an oil-water interface, positive charges and negative charges between a zwitterionic surfactant and an anionic surfactant are mutually attracted, electrostatic repulsive interaction between the same charges is weakened, the arrangement is compact on the interface, the adsorption capacity is increased, the surface interfacial activity is favorably increased, the hydrophobicity of an alkyl siloxane main chain in a hydrophobic group part on the surface of the polyether organosilicon modified silicon dioxide particles is stronger than that of a carbon chain formed by traditional methylene, and the polyether organosilicon modified silicon dioxide has stronger surface interfacial activity and can be rapidly adsorbed on a crude oil-water interface. The synergistic effect of the components washes the crude oil from the rock stratum sand and effectively solubilizes the crude oil, and finally improves the recovery ratio of the crude oil.
In the invention, the zwitterionic surfactant, the anionic surfactant and the polyether organosilicon modified silica particles are adopted for compounding, so that alkali-free compound flooding oil extraction is realized, and the problems of damage to stratum caused by alkali, corrosion to equipment and demulsification difficulty caused by the damage to stratum caused by alkali during field application are avoided. The total concentration of the surfactant and the nano particles is in the range of 0.01-1%, so that the surfactant and the nano particles have excellent interface performance, crude oil can be driven, and physical simulation oil displacement experiments show that the composite oil displacement agent can improve the recovery ratio by more than 10% on the basis of water displacement, and a better technical effect is achieved.
Drawings
FIG. 1 shows the microstructure of the polyether silicone modified silica particles obtained in example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials and sources used in the examples are as follows:
preparation of amphoteric surfactant:
Adding 0.5mol of fatty acid methyl ester (methyl palmitate or methyl oleate) and 1mol of amidation reagent N, N-dimethylpropane diamine into a reaction kettle, reacting for 8 hours at 140 ℃, vacuumizing to remove methanol and excessive N, N-dimethylpropane diamine generated by the reaction to obtain a tertiary amine product, adding 0.75mol of quaternary amination reagent sodium chloroacetate, reacting for 10 hours at 80 ℃, and recrystallizing and purifying by absolute ethyl alcohol to obtain the amphoteric surfactant (hexadecylaminocarboxybetaine or oleamide carboxyarboxybetaine).
Anionic surfactant preparation:
Adding fatty alcohol polyoxyethylene ether (tetradecyl alcohol polyoxyethylene ether or octadecyl alcohol polyoxyethylene ether) and NaOH into a reaction kettle, reacting for 3 hours at 65 ℃, then adding carboxylation reagent sodium chloroacetate or sulphonation reagent sodium 3-chloro-2-hydroxy propane sulfonate, heating to 85 ℃ and reacting for 8 hours. Wherein the fatty alcohol polyoxyethylene ether: naOH: carboxylation reagent or sulfonation reagent in the molar ratio of 1:1.5:2, then acidizing and washing, and performing oil-water separation, and further alkalizing the oil phase to obtain the anionic surfactant (sodium tetradecyl polyoxyethylene ether carboxylate or sodium octadecyl polyoxyethylene ether hydroxypropyl sulfonate).
The other compounds used in the examples are all commercially available.
Example 1 preparation of polyether Silicone modified silica particles
Adding 15mL of tetraethoxysilane into 13mL of a mixed solution of 25wt% ammonia water and 150mL of absolute ethyl alcohol, stirring at 30 ℃ for reaction for 12h, centrifugally collecting, washing with ethanol for three times, and vacuum drying at 60 ℃ to obtain silicon dioxide particles; dispersing 5g of silicon dioxide particles in 75mL of toluene, adding 5g of 3-chloropropyl triethoxysilane, reacting for 6 hours at 80 ℃, centrifugally collecting, washing with toluene for three times, and vacuum drying at 60 ℃ to obtain coupling agent modified silicon dioxide particles; dispersing 5g of coupling agent modified silicon dioxide particles in 75mL of acetonitrile, adding 0.8g of NaOH and 10.2g of polyether modified heptamethyltrisiloxane, reacting for 20 hours at 80 ℃, centrifugally collecting, washing with ethanol for three times, and vacuum drying at 60 ℃ to obtain polyether organosilicon modified silicon dioxide particles. The micro morphology of the polyether organosilicon modified silica particles is shown in figure 1, and the modified particle size is about 116nm.
Example 2 preparation of polyether Silicone modified silica particles
Adding 12mL of butyl orthosilicate into 10mL of mixed solution of 25wt% ammonia water and 180mL of anhydrous methanol, stirring and reacting for 8h at 20 ℃, centrifugally collecting, washing with ethanol for three times, and vacuum drying at 60 ℃ to obtain silicon dioxide particles; dispersing 5g of silica particles in 75mL of dimethylbenzene, adding 5g of 3-chloropropyl trimethoxysilane, reacting for 6 hours at 90 ℃, centrifugally collecting, washing with toluene for three times, and vacuum drying at 60 ℃ to obtain coupling agent modified silica particles; dispersing 5g of coupling agent modified silicon dioxide particles in 75mL of acetonitrile, adding 1g of NaOH and 15.8g of polyether modified octamethyltetrasiloxane, reacting for 20h at 80 ℃, centrifugally collecting, washing with ethanol for three times, and vacuum drying at 60 ℃ to obtain polyether organosilicon modified silicon dioxide particles. The particle size was about 95nm.
Example 3 preparation of surfactant/nanoparticle composite oil-displacing agent
1.2G of the polyether silicone modified silica obtained in example 1 was added to 1000g of a saline (6000 mg/LNaCl) solution of cetylamide carboxybetaine having a concentration of 0.2 wt.% sodium stearyl polyoxyethylene ether hydroxypropylsulfonate, wherein cetylamide carboxybetaine: the mass ratio of the sodium stearyl alcohol polyoxyethylene ether and the hydroxypropyl sulfonate is 1:1.5, and the surfactant/nano particle composite oil displacement agent is obtained after stirring and dispersing uniformly.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores of length 10cm, diameter 2.5cm and permeability 264mD at 50 ℃. Firstly, water flooding is carried out until the water content is 98%, after the water flooding is finished, 0.3pv (core pore volume) of the compound oil displacement agent is transferred, then the water flooding is carried out until the water content is 98%, and the crude oil recovery rate is improved by 17% on the basis of the water flooding.
Example 4 preparation of surfactant/nanoparticle composite oil-displacing agent
1G of the polyether silicone modified silica obtained in example 1 was added to 1000g of a saline (9000 mg/L NaCl) solution of oleic acid amide carboxybetaine having a concentration of 0.1% by weight of sodium tetradecanol polyoxyethylene ether carboxylate: the mass ratio of the sodium tetradecyl alcohol polyoxyethylene ether carboxylate is 1:0.8, and the surfactant/nano particle composite oil displacement agent is obtained after stirring and dispersing uniformly.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. Simulated flooding experiments were performed on cores with a length of 10cm, a diameter of 2.5cm, and a permeability of 309mD at 45 ℃. And after the water flooding is finished, transferring 0.3pv (core pore volume) of the compound oil displacement agent, and then, driving the water flooding to 98% of water, thereby improving the recovery ratio of the crude oil by 19% on the basis of the water flooding.
Example 5 preparation of surfactant/nanoparticle composite oil-displacing agent
1.1G of the polyether silicone modified silica obtained in example 2 was added to 1000g of a solution of cetylsulfbetaine, sodium stearyl polyoxyethylene ether hydroxypropylsulfonate in brine (15000 mg/LNaCl) having a concentration of 0.2% by weight, wherein cetylsulfbetaine: the mass ratio of the sodium stearyl alcohol polyoxyethylene ether and the hydroxypropyl sulfonate is 1:1, and the surfactant/nano particle composite oil displacement agent is obtained after stirring and dispersing uniformly.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores of length 10cm, diameter 2.5cm and permeability 248mD at 60 ℃. And after the water flooding is finished, transferring 0.3pv (core pore volume) of the compound oil displacement agent, and then, driving the water flooding to 98% of water, thereby improving the recovery ratio of crude oil by 14% on the basis of water flooding.
Example 6 preparation of surfactant/nanoparticle composite oil-displacing agent
1.1G of the polyether silicone modified silica obtained in example 2 was added to 1000g of a solution of hexadecylaminocarbobetaine at a concentration of 0.15% by weight, sodium dodecylbenzenesulfonate in brine (10000 mg/LNaCl), in which hexadecylaminocarbobetaine: the mass ratio of the sodium dodecyl benzene sulfonate is 1:1.2, and the surfactant/nano particle composite oil displacement agent is obtained after stirring and dispersing uniformly.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores of length 10cm, diameter 2.5cm and permeability 356mD at 45 ℃. Firstly, water flooding is carried out until the water content is 98%, after the water flooding is finished, 0.3pv (core pore volume) of the compound oil displacement agent is transferred, then the water flooding is carried out until the water content is 98%, and the crude oil recovery rate is improved by 15% on the basis of the water flooding.
Comparative example 1
A saline (6000 mg/L NaCl) solution of 0.2wt% cetyl amide carboxybetaine, sodium stearyl polyoxyethylene ether hydroxypropylsulfonate was prepared, wherein cetyl amide carboxybetaine: the mass ratio of the sodium stearyl alcohol polyoxyethylene ether hydroxypropyl sulfonate is 1:1.5.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores of 10cm length, 2.5cm diameter and 297mD permeability at 50 ℃. Firstly, water driving to 98% of water content, after the water driving is finished, transferring 0.3pv (core pore volume) of the solution, then, water driving to 98% of water content, and improving the recovery ratio of crude oil by 4.8% on the basis of water driving.
Comparative example 2
1.2G of the polyether organosilicon modified silica prepared in example 1 was added to 1000g of a 0.2wt% aqueous solution of cetyl amidocarboxybetaine (6000 mg/L NaCl) and stirred and dispersed uniformly to obtain a surfactant/nanoparticle dispersion.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores of length 10cm, diameter 2.5cm and permeability 328mD at 50 ℃. Firstly, water driving to 98% of water content, after the water driving is finished, transferring 0.3pv (core pore volume) of the dispersion liquid, then, water driving to 98% of water content, and improving the recovery ratio of crude oil by 6% on the basis of water driving.
Comparative example 3
1.2G of the polyether organosilicon modified silica prepared in example 1 was added to 1000g of a saline (6000 mg/L NaCl) solution of 0.2wt% sodium stearyl polyoxyethylene ether hydroxypropyl sulfonate, and stirred and dispersed uniformly to obtain a surfactant/nanoparticle dispersion.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores with a length of 10cm, a diameter of 2.5cm, and a permeability of 235mD at 50 ℃. Firstly, water driving to 98% of water content, after the water driving is finished, transferring 0.3pv (core pore volume) of the dispersion liquid, then, water driving to 98% of water content, and improving the crude oil recovery ratio by 5.7% on the basis of water driving.
Comparative example 4
Preparing a saline (6000 mg/L NaCl) solution of 0.32wt% of polyether modified heptamethyltrisiloxane, hexadecylamide carboxybetaine and sodium stearyl polyoxyethylene ether hydroxypropyl sulfonate, wherein the polyether modified heptamethyltrisiloxane: cetyl amidocarboxybetaine: the mass ratio of the sodium stearyl alcohol polyoxyethylene ether and the hydroxypropyl sulfonate is 1.5:1:1.5.
And carrying out an oil displacement experiment according to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method. A simulated flooding experiment was performed on cores with a length of 10cm, a diameter of 2.5cm, and a permeability of 300mD at 50 ℃. Firstly, water driving to 98% of water content, after the water driving is finished, transferring 0.3pv (core pore volume) of the solution, then, water driving to 98% of water content, and improving the recovery ratio of crude oil by 9.7% on the basis of water driving.
Claims (17)
1. The surfactant/nanoparticle composite oil displacement agent comprises a surfactant, nanoparticles and water, wherein the surfactant comprises a zwitterionic surfactant and an anionic surfactant, and the nanoparticles are polyether organosilicon modified silica particles; the nano particles are obtained by modifying silicon dioxide particles by components including polyether modified polysiloxane and a silane coupling agent.
2. The compound oil displacement agent according to claim 1, wherein,
The particle size of the nano particles is 10-300 nm; and/or the number of the groups of groups,
In the compound oil displacement agent, the mass ratio of the amphoteric ion surfactant to the anionic surfactant to the nano particles is 1 (0.01-100); and/or the number of the groups of groups,
The total concentration of the surfactant and the nano particles in the compound oil displacement agent is 0.01-1% by mass percent; and/or the number of the groups of groups,
The mineralization degree of the water is 0-50000 mg/L based on the weight of NaCl.
3. The compound oil displacement agent according to claim 2, wherein,
The particle size of the nano particles is 30-200 nm; and/or the number of the groups of groups,
In the compound oil displacement agent, the mass ratio of the amphoteric ion surfactant to the anionic surfactant to the nano particles is 1 (0.1-10) (0.4-2); and/or the number of the groups of groups,
The total concentration of the surfactant and the nano particles in the compound oil displacement agent is 0.01-0.5% by mass percent.
4. The compound oil displacement agent according to claim 1, wherein,
The structure of the amphoteric ion surfactant is as follows:
Wherein R 1 is a hydrocarbon group of C 6～C32 or a group of the structure R 1-CO-NH-R2 -, wherein R 1 is selected from hydrocarbon groups of C 6～C32 and R 2 is selected from alkylene groups of C 1～C10; r 2、R3 is independently selected from hydrocarbyl or substituted hydrocarbyl of C 1～C5, R 4 is selected from alkylene or hydroxy substituted alkylene of C 1～C4; x is selected from SO 3 - or COO -; and/or the number of the groups of groups,
The structural formula of the anionic surfactant is at least one of the formula (1) and the formula (2):
r 5 -YM type (1)
R 5-O-(R7-O)n-R6 -YM (2)
Wherein R 5 is selected from the hydrocarbon group of C 6～C20; r 6 is selected from alkylene or hydroxy-substituted alkylene of C 1～C4; y is selected from SO 3 - or COO -, and M is selected from a cation or a cationic group; r 7 is selected from the group consisting of linear or branched alkylene of C 2～C4 and n is selected from the integers of 1 to 30.
5. The compound oil-displacing agent as claimed in claim 4, wherein,
The amphoteric surfactant is at least one selected from dodecyl betaine, hexadecyl amide carboxyl betaine, hexadecyl sulfo betaine, oleamide carboxyl betaine, erucic acid amide carboxyl betaine and docosyl betaine; and/or the number of the groups of groups,
The anionic surfactant is at least one selected from alpha-olefin sodium sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium tetradecyl polyoxyethylene ether carboxylate, sodium octadecyl polyoxyethylene ether hydroxypropyl sulfonate and sodium octadecyl benzene sulfonate.
6. The compound oil-displacing agent as claimed in claim 5, wherein,
The amphoteric surfactant is at least one selected from hexadecylamide carboxyl betaine, oleamide carboxyl betaine and hexadecyl sulfobetaine; and/or the number of the groups of groups,
The anionic surfactant is at least one selected from sodium stearyl alcohol polyoxyethylene ether hydroxypropyl sulfonate, sodium tetradecyl alcohol polyoxyethylene ether carboxylate and sodium dodecyl benzene sulfonate.
7. The compound oil displacement agent according to claim 1, wherein,
The silane coupling agent is selected from chloralkyl silane coupling agent and/or,
The polyether modified polysiloxane is at least one selected from polyether modified hexamethyltrisiloxane, polyether modified heptamethyltrisiloxane, polyether modified tetramethyl cyclotetrasiloxane, polyether modified octamethyl tetrasiloxane, polyether modified decamethyl pentasiloxane and polyether modified hydrogen-containing silicone oil.
8. The compound oil-displacing agent as claimed in claim 7, wherein,
The silane coupling agent is at least one selected from 3-chloropropyl trimethoxysilane and 3-chloropropyl triethoxysilane; and/or the number of the groups of groups,
The polyether modified polysiloxane is at least one selected from polyether modified heptamethyltrisiloxane and polyether modified octamethyltetrasiloxane.
9. A method for preparing the surfactant/nanoparticle composite oil-displacing agent according to any one of claims 1 to 8, comprising the steps of dissolving components including the amphoteric surfactant and the anionic surfactant in water, adding the polyether organosilicon modified silica particles into the aqueous solution of the surfactant, and uniformly dispersing to obtain the surfactant/nanoparticle composite oil-displacing agent.
10. The method of preparing according to claim 9, wherein the method of preparing polyether silicone modified silica particles comprises:
step a, dispersing nano silicon dioxide particles in a solvent S 1, adding a silane coupling agent, heating and stirring for reaction to obtain coupling agent modified silicon dioxide particles; the solvent S 1 is selected from organic solvents;
step b, dispersing the coupling agent modified silicon dioxide particles obtained in the step a in a solvent S 2, adding polyether modified polysiloxane, and heating and stirring to react to obtain the polyether organosilicon modified silicon dioxide particles; the solvent S 2 is selected from organic solvents.
11. The method according to claim 10, wherein,
The particle size of the nano silicon dioxide particles is 10-300 nm; and/or the number of the groups of groups,
The solvent S 1 is at least one selected from toluene, xylene and ethanol; and/or the number of the groups of groups,
The solvent S 2 is at least one selected from N, N-dimethylformamide, acetonitrile and toluene; and/or the number of the groups of groups,
In the step a, the mass ratio of the nano silicon dioxide particles to the silane coupling agent to the solvent S 1 is (2-15): (2-23): 100; and/or the number of the groups of groups,
In the step b, the mass ratio of the coupling agent modified silicon dioxide to the polyether modified polysiloxane to the solvent S 2 is (2-15): (5-60): 100.
12. The method according to claim 11, wherein,
The particle size of the nano silicon dioxide particles is 30-200 nm; and/or the number of the groups of groups,
In the step a, the mass ratio of the nano silicon dioxide particles, the silane coupling agent and the solvent S 1 is (5-10): (5-12): 100; and/or the number of the groups of groups,
In the step b, the mass ratio of the coupling agent modified silicon dioxide to the polyether modified polysiloxane to the solvent S 2 is (5-10): (10-38): 100.
13. The method according to claim 10, wherein,
The reaction temperature in the step a is 60-150 ℃ and the reaction time is 4-30 h; and/or the number of the groups of groups,
The reaction temperature in the step b is 60-150 ℃ and the reaction time is 8-30 h; and/or the number of the groups of groups,
In step b, an alkaline compound is also required to be added; and/or the number of the groups of groups,
The solid obtained by the reaction in the steps a-b is also required to be washed and dried.
14. The method of claim 13, wherein the process comprises,
The reaction temperature in the step a is 80-120 ℃ and the reaction time is 6-20 h; and/or the number of the groups of groups,
The reaction temperature in the step b is 80-120 ℃ and the reaction time is 16-24 h.
15. The method of claim 13, wherein the process comprises,
The basic compound added in step b is selected from inorganic basic compounds; and/or the number of the groups of groups,
The mass ratio of the alkaline compound and the solvent S 2 added in the step b is (0.3-4): 100; and/or the number of the groups of groups,
The solvent adopted in the step a-b is at least one selected from methanol, ethanol, toluene and acetone; and/or the number of the groups of groups,
The drying temperature in the steps a-b is 20-100 ℃.
16. The method according to claim 15, wherein,
The alkaline compound added in the step b is at least one selected from sodium hydroxide and potassium hydroxide; and/or the number of the groups of groups,
The mass ratio of the alkaline compound and the solvent S 2 added in the step b is (0.8-2.6): 100; and/or the number of the groups of groups,
The solvent adopted in the washing in the steps a-b is at least one selected from ethanol and toluene; and/or the number of the groups of groups,
The drying temperature in the steps a-b is 40-80 ℃.
17. Use of the surfactant/nanoparticle composite oil-displacing agent of any one of claims 1 to 8 or the surfactant/nanoparticle composite oil-displacing agent prepared by the method of any one of claims 9 to 16 in tertiary oil recovery.
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