CN116254100A - Composite surfactant and preparation method thereof - Google Patents
Composite surfactant and preparation method thereof Download PDFInfo
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- CN116254100A CN116254100A CN202111496595.0A CN202111496595A CN116254100A CN 116254100 A CN116254100 A CN 116254100A CN 202111496595 A CN202111496595 A CN 202111496595A CN 116254100 A CN116254100 A CN 116254100A
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- surfactant
- hydrocarbon group
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- alkyl
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 6
- -1 alkyl aniline Chemical compound 0.000 claims abstract description 67
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 16
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 12
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims abstract description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims abstract description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 10
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
- 208000014674 injury Diseases 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 33
- 239000003921 oil Substances 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 24
- 239000010779 crude oil Substances 0.000 description 24
- 238000006073 displacement reaction Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- IXEGRINNWXKNJO-UHFFFAOYSA-N n-hexadecylaniline Chemical compound CCCCCCCCCCCCCCCCNC1=CC=CC=C1 IXEGRINNWXKNJO-UHFFFAOYSA-N 0.000 description 9
- SOANRMMGFPUDDF-UHFFFAOYSA-N 2-dodecylaniline Chemical compound CCCCCCCCCCCCC1=CC=CC=C1N SOANRMMGFPUDDF-UHFFFAOYSA-N 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 8
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 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 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 4
- GCULWAWIZUGXTO-UHFFFAOYSA-N n-octylaniline Chemical compound CCCCCCCCNC1=CC=CC=C1 GCULWAWIZUGXTO-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- YXQMBBJITUIBDQ-UHFFFAOYSA-M dodecyl(triethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](CC)(CC)CC YXQMBBJITUIBDQ-UHFFFAOYSA-M 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DPYHFDVRNNQVON-UHFFFAOYSA-N 1,1-dichloroethane;sulfur trioxide Chemical compound CC(Cl)Cl.O=S(=O)=O DPYHFDVRNNQVON-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IXHUMEGZQJOZRN-UHFFFAOYSA-N benzenesulfonic acid;methoxymethane Chemical compound COC.OS(=O)(=O)C1=CC=CC=C1 IXHUMEGZQJOZRN-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ITJSVDCZHCYXQE-UHFFFAOYSA-N toluene;hydroiodide Chemical compound I.CC1=CC=CC=C1 ITJSVDCZHCYXQE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a composite surfactant and a preparation method thereof, wherein the composite surfactant comprises an anionic surfactant and a cationic surfactant; wherein the mass ratio of the anionic surfactant to the cationic surfactant is (0.01-5): 0.01-5, the anionic surfactant is selected from alkyl aniline polyether benzene sulfonate, and the cationic surfactant is selected from any one of quaternary ammonium salt or quaternary ammonium base. The composite surfactant has the advantages of high interfacial activity, strong temperature resistance and salt resistance, strong calcium and magnesium ion resistance, does not contain alkali, effectively avoids oil layer injury, and has good application prospect.
Description
Technical Field
The invention relates to a compound surfactant and a preparation method thereof.
Background
Chemical flooding is an important means of increasing crude oil recovery, with surfactants playing a vital role. The surfactants currently used in oilfield sites are mostly a complex of anionic surfactants, nonionic surfactants, and in use, an auxiliary base is added to reduce the oil/water interfacial tension. As patent CN101024764a, a surfactant for oilfield heavy oil well is provided, which is composed of water, caustic soda flakes, ethanol, oleic acid, alkylphenol ethoxylates, and sodium dodecyl benzene sulfonate. The surfactant has more problems, mainly including poor surfactant activity and low oil displacement efficiency, and meanwhile, the produced liquid is difficult to demulsifie and the sewage is difficult to treat because the surfactant system is too complex; in addition, the oil displacement system contains inorganic alkali, so that the oil displacement system causes damage to stratum and oil well, and causes the problems of equipment corrosion, pipeline corrosion and the like; surfactants have limited resistance to high temperatures, high salts and high mineralization.
In recent years, research shows that the mixed system aqueous solution of the anionic and cationic surfactants has a plurality of special properties, such as that the anionic and cationic surfactants have strong electrostatic action and interaction between hydrophobic carbon chains in the aqueous solution, so that association between two surfactants with different charges is promoted, micelles are easily formed in the solution, and the interfacial activity is higher than that of a single surfactant. Yojun et al (university of northwest journal, 30 (1): 28-31) studied that cetyltrimethylammonium bromide (CTAB) and Sodium Dodecyl Sulfate (SDS) mixed systems have a solubilizing effect. Huang Hongdu et al (journal of Petroleum and Natural gas, 29 (4): 101-104) studied the interfacial tension of anionic surfactants such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate, etc., and cetyltrimethylammonium bromide, alkali complex systems and concluded that: the addition of the cationic surfactant improves the interfacial activity of petroleum carboxylate, alkylbenzenesulfonate and petroleum sulfonate. The research results show that the anionic and cationic surfactant composite system has a certain effect on reducing the interfacial tension of oil and water and improving the oil displacement efficiency. However, the interfacial properties are still to be improved, and alkali is adopted in the system, so that the problems of damage to stratum and oil well caused by alkali, equipment and pipeline corrosion, difficulty in demulsification and the like cannot be avoided.
The invention relates to a composite surfactant, which comprises a novel anionic and nonionic sulfonate surfactant, namely alkyl aniline polyether benzene sulfonate and a cationic surfactant, has the advantages of high interfacial activity, strong temperature resistance and salt resistance and strong calcium and magnesium ion resistance, does not contain alkali, effectively avoids oil layer injury, and has good application prospect.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the alkali-containing oil displacement system of the surfactant in the prior art is easy to cause oil reservoir damage and has low oil displacement efficiency, and the novel composite surfactant is provided, and has the characteristics of low oil reservoir damage and high oil displacement efficiency.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a complex surfactant comprising an anionic surfactant and a cationic surfactant; wherein the mass ratio of the anionic surfactant to the cationic surfactant is (0.01-5): 0.01-5, the anionic surfactant is selected from alkyl aniline polyether benzene sulfonate, and the cationic surfactant is selected from any one of quaternary ammonium salt or quaternary ammonium base.
In a preferred embodiment, the cationic surfactant is selected from at least one of the quaternary ammonium salts represented by formula (I):
in the formula (I), R 4 ，R 5 ，R 6 ，R 6 H, C each independently 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; x is X h- Is an anion, and h is the number of negative charges of the anion.
In a preferred embodiment, the X h- Is F - 、Cl - 、Br - 、I - 、OH - 、NO 3 - 、CH 3 COO - 、HO-C 6 H 4 -COO - 、CH 3 -C 6 H 4 -SO 3 - 、CH 3 SO 3 - 、HO-CH 2 COO - 、CH 3 CH(OH)COO - Any one of the following.
In a further preferred embodiment, said R 4 Is C 8 ～C 24 R is a hydrocarbon group of 5 ，R 6 ，R 7 Is C 1 ～C 8 Is a hydrocarbon group or a substituted hydrocarbon groupA base.
In a preferred embodiment, the alkylaniline polyether-benzene sulfonate has the structure of formula (II):
in the formula (II), R 1 And R is 2 Independently selected from H, C 1 -C 40 Is a hydrocarbon group or
And not simultaneously H, R 3 Independently at each occurrence selected from H, C 1 -C 10 C is a hydrocarbon group of (C) 1 -C 10 Carbonyl group, C of (2) 1 -C 10 Alkyl sulfonic acid group, C 1 -C 10 Alkyl alcohol sulfonic acid group, C 1 -C 10 Alkyl carboxylic acid groups of (C) and-SO 3 M，-(Polym) 1 -is- (PO) x1 -、-(EO) y1 -、-(BO) z1 -a combination of one or more of the following; - (Poly) 2 -is- (PO) x2 -、-(EO) y2 -、-(BO) z2 -a combination of one or more of the following; x is x 1 、x 2 、y 1 、y 2 、z 1 And z 2 Each independently selected from any integer between 0 and 50, and x 1 +x 2 ＝0～50，y 1 +y 2 ＝1～50，z 1 +z 2 =0 to 50; and wherein PO is propoxy, EO is ethoxy, BO is butoxy, M is selected from any one of alkali metal and alkaline earth metal;
in a further preferred embodiment, said R 1 Is C 6 -C 30 R is a hydrocarbon group of 2 H, C of a shape of H, C 1 -C 30 Is a hydrocarbon group or-N ((PO) x1 (EO) y1 R 3 ) 2 ，R 3 Is H, -CH 3 、-CH 2 CH 3 、-CH 2 SO 3 (M) n 、-CH 2 (CHOH)SO 3 (M) n 、-CH 2 COO(M) n or-SO 3 (M) n ，x 1 +x 2 ＝0～30，y 1 +y 2 ＝1～30，z 1 +z 2 ＝0～20。
In a still further preferred embodiment, said R 1 Is C 6 -C 20 Preferably R 1 Is C 6 -C 20 Alkyl of (a); r is R 2 Is H or C 1 -C 30 Alkyl of R 3 Selected from H, -CH 3 or-CH 2 CH 3 ，x 1 +x 2 ＝0～20，y 1 +y 2 ＝1～20，z 1 +z 2 =0 to 10, and m is selected from any one of sodium ion, potassium ion, calcium ion, or magnesium ion.
In a still further preferred embodiment, - (Polym) 1 -is- (PO) x1 - (denoted as A), - (EO) y1 - (B), - (BO) z1 Any one or more combinations of (denoted as C), when- (Poly) 1 Two or more of them may be combined by one or more of random copolymerization or block copolymerization of two or three, and one or more of them may be arbitrarily arranged and combined in block copolymerization, for example AB, BA, AC, CA, BC, CB, ABC, ACB, BAC, BCA, CAB, CBA, etc.; - (Poly) 2 -as described above may also be- (PO) x2 -、-(EO) y2 -、-(BO) z2 The combination of one or more of them may be a random copolymerization of two or three or a combination of one or more of them, or may be any of the above-mentioned arrangements in the case of block copolymerization.
In the most preferred embodiment, - (Poly) 1 -is- (PO) x1 -(EO) y1 -，-(Polym) 2 -is- (PO) x2 -(EO) y2 -。
The polyether chain in the structure of the surfactant of the invention is connected with the benzene ring through N atom, and meanwhile, the hydrophobic long chain (R 1 And R is 2 ) And is also directly connected with benzene ring, has special structure, and experiments show that the special structure can bring very excellent effect.
The second technical problem to be solved by the invention is to provide a preparation method of a composite surfactant corresponding to one of the technical problems, which comprises the following steps:
step 1, using alkyl aniline as an initiator, reacting with an epoxy compound, and optionally carrying out end capping treatment after the reaction is finished to obtain alkyl aniline polyether;
and step 2, carrying out sulfonation treatment on the alkyl aniline polyether to obtain the alkyl aniline polyether benzene sulfonate oil displacement surfactant.
And 3, mixing the anionic surfactant, namely the alkyl aniline polyether benzene sulfonate and the cationic surfactant to obtain the composite surfactant.
In a preferred embodiment, the hydrocarbylaniline has the formula: r is R 1 -Ph-NH 2 Wherein Ph represents phenyl, R 1 As claimed in any one of the preceding claims.
In a preferred embodiment, in step 1, the epoxy compound is selected from C 2 ～C 6 Preferably propylene oxide and/or ethylene oxide.
Preferably, in step 1, propylene oxide and ethylene oxide are reacted sequentially.
In a further preferred embodiment, in step 1, the molar ratio of the epoxy compound to the hydrocarbylaniline is (1 to 150): 1, preferably (1 to 90): 1, more preferably (1 to 60): 1, still more preferably (1 to 40): 1 or (2 to 40): 1.
In a preferred embodiment, step 1 is carried out in the presence of a basic catalyst.
In a further preferred embodiment, the basic catalyst is selected from at least one of alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkali metal oxides, preferably from alkali metal hydroxides and/or alkaline earth metal hydroxides.
In a still further preferred embodiment, the basic catalyst is used in an amount of 0.1wt% to 10wt%, preferably 0.5wt% to 5.0wt%.
In a preferred embodiment, in step 1, the reaction conditions are: the reaction temperature is 140-200 ℃ and the reaction pressure is 0-5 MPa.
In a further preferred embodiment, in step 1, the reaction conditions are: the reaction temperature is 140-160 ℃, and the reaction pressure is 0.2-2 MPa.
In a preferred embodiment, in step 1, the capping agent is selected from R' 3 X or R'. 3 -X’-R” 3 Wherein R 'is' 3 Is C 1 -C 10 Or C (C) is a hydrocarbon group 1 -C 10 X is selected from halogen or hydroxy, when X is hydroxy, R' 3 Is C 1 -C 10 Carbonyl of (a); r' R " 3 Selected from C 1 -C 10 X' is selected from O; preferably halogen is F, cl or Br, R' 3 Is C 1 -C 10 Alkyl, alkenyl or phenylalkyl; more preferably, the end-capping agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, vinyl iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, benzoyl chloride.
In a still further preferred embodiment, the molar ratio of the capping agent to the alkylaniline is from (2 to 2.6): 1, preferably from (2.04 to 2.4): 1.
In a preferred embodiment, in step 3, unreacted alkylaniline and epoxide compounds in the reaction system are removed before the capping treatment, preferably at 80 to 110℃and preferably at 80 to 110℃under vacuum or nitrogen bubbling.
In a preferred embodiment, in step 2, the sulfonation treatment is performed with a sulfonating agent selected from at least one of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide.
In a further preferred embodiment, in step 2, the molar ratio of the hydrocarbylaniline polyether to the sulphonating agent is from 1 (1 to 8), preferably from 1 (1 to 5).
In a still further preferred embodiment, step 2 comprises the sub-steps of:
step 2-1, mixing the alkyl aniline polyether and a sulfonating reagent, and performing sulfonation reaction for 0.5-10 hours at 20-80 ℃;
and 2-2, regulating the pH value to 10-14, and carrying out hydrolysis reaction for 0.5-5 hours to obtain the alkyl aniline polyether benzene sulfonate surfactant.
In a preferred embodiment, the sulfonation reaction of step 2-1 proceeds as follows: and the reaction is carried out for 1 to 3 hours at the temperature of between 30 and 60 ℃.
In a preferred embodiment, the complex surfactant contains water selected from any one or more of mineralized water having a total degree of mineralization ranging from 0 to 300000mg/L, oilfield injection water, formation water, sea water, rainwater and river water, preferably mineralized water having a total degree of mineralization ranging from 80000 to 200000 mg/L. The composition of the five-injection water in the crude oil field adopted in the embodiment of the invention is shown in the table 1 in consideration of convenience in construction, water resource saving and the like.
The composite surfactant has good surface and interface activities and good salt resistance, and can form lower interfacial tension on an oil-water interface, so that the composite surfactant is used for chemical flooding enhanced oil recovery and has wide application prospect and practical significance.
The invention also aims to provide the application of the composite surfactant in the improvement of the crude oil recovery ratio.
In a preferred embodiment, the method of enhancing recovery using the complex surfactant comprises: and injecting the composite surfactant into a crude oil stratum to displace crude oil.
In a preferred embodiment, the complex surfactant and water are injected into the formation as a displacement fluid (e.g., an aqueous solution); the concentration of the complex surfactant is preferably 0.01 to 10.0% by weight based on the total weight of water and the complex surfactant.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite surfactant has the advantages of good compatibility, good salt resistance, and especially good calcium and magnesium ion resistance;
(2) The inventionThe composite surfactant has high interfacial activity, and can reach 10 under the condition of no alkali and high mineralization -3 The advantage of ultra-low interfacial tension of mN/m, thereby improving the recovery ratio of crude oil.
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 used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
In examples and comparative examples, crude oil from the crude oil field pica and Hu Wu from the crude oil field were used to inject water.
[ example 1 ]
a) To a reactor equipped with a condensing unit, a stirring unit and a gas disperser were added 1.0mol of triacontylaniline and 2.5g of sodium hydroxide, and the mixture was stirred and reacted for 1 hour while being heated to 85℃by introducing nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 6.1mol of propylene oxide and 10.2mol of ethylene oxide in sequence, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the system is purged by nitrogen, and is neutralized and dehydrated after being cooled, so that 0.98mol of triacontyl aniline polyoxypropylene (6) polyoxyethylene (10) ether is obtained.
d) Dissolving 0.98mol of triacontyl aniline polyoxypropylene (6) polyoxyethylene (10) ether synthesized in the step c) into 500ml of dichloroethane, adding the obtained solution into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.3mol of 20wt% sulfur trioxide dichloroethane solution, controlling the reaction temperature to be 15 ℃, continuously reacting for 0.5 hour after dripping, adding sodium hydroxide to adjust the pH to 13, and hydrolyzing for 2 hours to obtain 0.81mol of triacontyl aniline polyoxypropylene (6) polyoxyethylene (10) ether sodium benzenesulfonate.
c) The triacontyl aniline polyoxypropylene (6) polyoxyethylene (10) ether sodium benzenesulfonate and tetrabutylammonium chloride are uniformly mixed according to the mol ratio of 3.5:1, and then are dissolved in water to prepare a solution with the weight percent of 0.3 percent, so as to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of Complex surfactant Performance
a) Interfacial tension evaluation
The interfacial tension results between the above-mentioned compound surfactant and the crude oil of the crude oil field are shown in Table 3 using a TX-500C rotary drop interfacial tension meter produced by Texas university of America at a rotation speed of 4500 rpm at 80 ℃.
b) Evaluation of oil displacement experiment
According to the physical simulated oil displacement effect test of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method, a simulated oil displacement experiment is carried out on a core with the length of 30cm, the diameter of 2.5cm and the permeability of 1.5m < 2 > -85 ℃. The water flooding is carried out by injecting water until the water content reaches 98%, after the water flooding is finished, 0.3pv (core pore volume) of the composite surfactant is transferred, and then the water flooding is carried out until the water content reaches 98%, and the result of improving the crude oil recovery ratio is shown in Table 4.
[ example 2 ]
a) To a reactor equipped with a condensing unit, a stirring unit and a gas disperser were charged 1.0mol of dodecylaniline and 2.5g of sodium hydroxide, and the reaction was stirred for 1 hour while heating to 85℃with nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 6.0mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the system is purged by nitrogen, and is neutralized and dehydrated after being cooled, so that 0.99mol of dodecylaniline polyoxyethylene (6) ether is obtained.
b) The obtained dodecylaniline polyoxyethylene (6) ether is dissolved in benzene solvent, sodium hydroxide is added according to the proportion of 1:3, alkalization is carried out for 1 hour at 60 ℃, carboxylation reagent sodium chloroacetate is added according to the proportion of 1:2.5, and reaction is carried out for 8 hours, thus obtaining 0.89mol of dodecylaniline polyoxyethylene (6) ether dicarboxylic acid sodium.
c) Adding 0.89mol of sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylate synthesized in the step b) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 1.5mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 30 ℃, continuing to react for 1 hour after the dripping is finished, and adding sodium hydroxide to adjust the pH value to 9 to obtain 0.75mol of sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylate sodium benzenesulfonate.
d) Uniformly mixing sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylic acid sodium benzenesulfonate and dodecyl triethyl ammonium chloride according to a molar ratio of 2.1:1, and then dissolving the mixture in water to prepare a solution with the concentration of 0.5wt% to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of Complex surfactant Performance
The performance evaluation method was the same as in example 1, except that the composition of the complex surfactant was different. For comparison, the compositions of the complex surfactants are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 3 ]
a) To a reactor equipped with a condensing unit, a stirring unit and a gas disperser were charged 1.0mol of dodecylaniline and 2.5g of sodium hydroxide, and the reaction was stirred for 1 hour while heating to 85℃with nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 6.0mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the system is purged by nitrogen, and is neutralized and dehydrated after being cooled, so that 0.99mol of dodecylaniline polyoxyethylene (6) ether is obtained.
b) The obtained dodecylaniline polyoxyethylene (6) ether is dissolved in benzene solvent, sodium hydroxide is added according to the proportion of 1:3, alkalization is carried out for 1 hour at 60 ℃, carboxylation reagent sodium chloroacetate is added according to the proportion of 1:2.5, and reaction is carried out for 8 hours, thus obtaining 0.89mol of dodecylaniline polyoxyethylene (6) ether dicarboxylic acid sodium.
c) Adding 0.89mol of sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylate synthesized in the step b) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 1.5mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 30 ℃, continuing to react for 1 hour after the dripping is finished, and adding sodium hydroxide to adjust the pH value to 9 to obtain 0.75mol of sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylate sodium benzenesulfonate.
d) Uniformly mixing sodium dodecyl aniline polyoxyethylene (6) ether dicarboxylic acid sodium benzenesulfonate and octadecyl trimethyl ammonium chloride according to a molar ratio of 2.1:1, and then dissolving the mixture in water to prepare a solution with the concentration of 0.5wt% to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of Complex surfactant Performance
The performance evaluation method was the same as in example 1, except that the composition of the complex surfactant was different. For comparison, the compositions of the complex surfactants are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 4 ]
a) 1.0mol of hexadecylaniline and 2.5g of sodium hydroxide were charged into a reactor equipped with a condensing apparatus, a stirring apparatus and a gas disperser, and the reaction was stirred while heating to 85℃with nitrogen gas for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 8.2mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the nitrogen is used for blowing the system, 2.4 mol of methyl iodide is added, the reaction is carried out for 1 hour at 90 ℃, and 0.99mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether is obtained after the neutralization and dehydration are carried out after cooling.
b) Adding 0.99mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether synthesized in the step a) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.5mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 30 ℃, continuing to react for 1 hour after dripping is finished, adding sodium hydroxide to adjust the pH to be 12, and carrying out hydrolysis reaction for 2 hours to obtain 0.78mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether sodium benzenesulfonate.
c) The sodium cetyl aniline polyoxyethylene (8) dimethyl ether benzene sulfonate and cetyl dimethyl benzyl ammonium chloride are uniformly mixed according to the mol ratio of 6.2:1, and then are dissolved in water to prepare a solution with the weight percent of 0.5 percent, so as to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of Complex surfactant Performance
The performance evaluation method was the same as in example 1, except that the composition of the complex surfactant was different. For comparison, the compositions of the complex surfactants are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 5 ]
a) 1.0mol of hexadecylaniline and 2.5g of sodium hydroxide were charged into a reactor equipped with a condensing apparatus, a stirring apparatus and a gas disperser, and the reaction was stirred while heating to 85℃with nitrogen gas for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 8.2mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the nitrogen is used for blowing the system, 2.4 mol of methyl iodide is added, the reaction is carried out for 1 hour at 90 ℃, and 0.99mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether is obtained after the neutralization and dehydration are carried out after cooling.
b) Adding 0.99mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether synthesized in the step a) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.5mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 30 ℃, continuing to react for 1 hour after dripping is finished, adding sodium hydroxide to adjust the pH to be 12, and carrying out hydrolysis reaction for 2 hours to obtain 0.78mol of hexadecyl aniline polyoxyethylene (8) dimethyl ether sodium benzenesulfonate.
c) The hexadecyl aniline polyoxyethylene (8) dimethyl ether sodium benzenesulfonate and the docosa trimethyl ammonium hydroxide are uniformly mixed according to the mol ratio of 10.3:1, and then are dissolved in water to prepare a solution with the weight percent of 0.5 percent, so as to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of Complex surfactant Performance
The performance evaluation method was the same as in example 1, except that the composition of the complex surfactant was different. For comparison, the compositions of the complex surfactants are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 6 ]
a) To a reactor equipped with a condensing unit, a stirring unit and a gas disperser were charged 1.0mol of octylaniline and 2.5g of sodium hydroxide, and the reaction was stirred for 1 hour while heating to 85℃with nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging with nitrogen for 4 times to remove air in the system, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing 30.1mol of propylene oxide and 16.1mol of ethylene oxide in sequence, and controlling the pressure to be less than or equal to 0.40MPa for etherification reaction; after the reaction is finished, the system is purged by nitrogen, and is neutralized and dehydrated after being cooled, so that 0.98mol of octyl aniline polyoxypropylene (30) polyoxyethylene (16) ether is obtained.
b) Adding 0.98mol of octyl aniline polyoxypropylene (30) polyoxyethylene (16) ether synthesized in the step a) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.0mol of 20% fuming sulfuric acid, controlling the reaction temperature to be 50 ℃, continuing to react for 1 hour after dripping, washing with water, extracting to remove redundant acid, adding organic sodium hydroxide to adjust the pH to 9, and obtaining 0.87mol of sodium octyl aniline polyoxypropylene (30) polyoxyethylene (16) ether disulfonate sodium benzenesulfonate.
c) The sodium benzene sulfonate of sodium polyoxyethylene (16) ether disulfonate and the didodecyl dimethyl ammonium chloride of octyl aniline polyoxypropylene (30) are uniformly mixed according to the mol ratio of 8.5:1, and then are dissolved in water to prepare a solution with the weight percent of 0.5 percent, so as to obtain the yin-yang composite surfactant. The composite surfactant is used for interfacial tension evaluation and oil displacement experiments. The compositions of five injections of water in the crude oil field used in all examples and comparative examples of the present invention are shown in Table 1. The composition of the complex surfactant is listed in table 2 for comparison.
2. Evaluation of surfactant Performance
The performance evaluation method was the same as in example 1, except that the composition of the complex surfactant was different. For comparison, the compositions of the complex surfactants are shown in Table 2, and the evaluation results are shown in Table 3.
[ comparative example 1 ]
The petroleum sodium sulfonate (Daqing oil refinery) and dodecyl triethyl ammonium chloride are mixed evenly according to the mol ratio of 8.5:1, and then are dissolved in five-injection water of the crude oil field to prepare 0.5wt% solution, thus obtaining the surfactant composition. The surfactant composition is used for interfacial tension evaluation and oil displacement experiments.
The evaluation method was the same as in example 1, and an interfacial tension of 0.054mN/m was measured between the surfactant composition and the crude oil in the crude oil field, and an enhanced oil recovery of 3.5% was measured.
[ comparative example 2 ]
Synthesis of C according to the procedure of example 1 of patent 200410096431.9 16-18 The alkyl benzene sulfonate is uniformly mixed according to the mol ratio of 8.5:1, and then is dissolved in five-injection water of an original oilfield to prepare a solution with the concentration of 0.5wt percent, so as to obtain the surfactant composition. The surfactant composition is used for interfacial tension evaluation and oil displacement experiments.
Evaluation method the same as in example 1, an interfacial tension of 0.038mN/m was established between the surfactant composition and the crude oil in the crude oil field, and an enhanced oil recovery of 4.1% was measured.
Five-injection water for crude oil field
| Project | Na + +K + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | TDS |
| mg/L | 50620 | 796 | 5355 | 97506 | 728 | 532 | 155537 |
Table 2 examples 1-6 Complex surfactant compositions
Table 3 examples 1-6 Complex surfactant Performance
| Examples | Interfacial tension (mN/m) | Enhanced recovery (%) |
| 1 | 0.0061 | 7.8 |
| 2 | 0.00037 | 9.6 |
| 3 | 0.00018 | 10.2 |
| 4 | 0.00022 | 11.2 |
| 5 | 0.00041 | 9.5 |
| 6 | 0.0051 | 8.2 |
Claims (10)
1. A complex surfactant comprising an anionic surfactant and a cationic surfactant; wherein the mass ratio of the anionic surfactant to the cationic surfactant is (0.01-5): 0.01-5, the anionic surfactant is selected from alkyl aniline polyether benzene sulfonate, and the cationic surfactant is selected from any one of quaternary ammonium salt or quaternary ammonium base.
2. The complex surfactant of claim 1, wherein the quaternary ammonium salt is selected from at least one of the formulae (I):
in the formula (I), R 4 ，R 5 ，R 6 ，R 6 H, C each independently 1 ～C 30 Is a hydrocarbon group or a substituted hydrocarbon group; x is X h- Is an anion, and h is the number of negative charges of the anion.
3. The complex surfactant of claim 2, wherein X is h- Is F - 、Cl - 、Br - 、I - 、OH - 、NO 3 - 、CH 3 COO - 、HO-C 6 H 4 -COO - 、CH 3 -C 6 H 4 -SO 3 - 、CH 3 SO 3 - 、HO-CH 2 COO - 、CH 3 CH(OH)COO - Any one of the following.
4. The complex surfactant of claim 2, wherein R is 4 Is C 8 ～C 24 R is a hydrocarbon group of 5 ，R 6 ，R 7 Is C 1 ～C 8 Or a substituted hydrocarbon group.
5. The compound surfactant of claim 1, wherein the hydrocarbylaniline polyether benzene sulfonate has the structure of formula (II):
in the formula (II), R 1 And R is 2 Independently selected from H, C 1 -C 40 Is a hydrocarbon group or
And not simultaneously H, R 3 Independently at each occurrence selected from H, C 1 -C 10 C is a hydrocarbon group of (C) 1 -C 10 Carbonyl group, C of (2) 1 -C 10 Alkyl sulfonic acid group, C 1 -C 10 Alkyl alcohol sulfonic acid group, C 1 -C 10 Alkyl carboxylic acid groups of (C) and-SO 3 M，-(Polym) 1 -is- (PO) x1 -、-(EO) y1 -、-(BO) z1 -a combination of one or more of the following; - (Poly) 2 -is- (PO) x2 -、-(EO) y2 -、-(BO) z2 -a combination of one or more of the following; x is x 1 、x 2 、y 1 、y 2 、z 1 And z 2 Each independently selected from any integer between 0 and 50, and x 1 +x 2 ＝0～50，y 1 +y 2 ＝1～50，z 1 +z 2 =0 to 50; and wherein PO is propoxy, EO is ethoxy, BO is butoxy, and M is any one of alkali metal and alkaline earth metal.
6. The complex surfactant of claim 5, wherein R is 1 Is C 6 -C 30 R is a hydrocarbon group of 2 H, C of a shape of H, C 1 -C 30 Is a hydrocarbon group or
R 3 Is H, -CH 3 、-CH 2 CH 3 、-CH 2 SO 3 (M) n 、-CH 2 (CHOH)SO 3 (M) n 、-CH 2 COO(M) n or-SO 3 (M) n ，x 1 +x 2 ＝0～30，y 1 +y 2 ＝1～30，z 1 +z 2 ＝0～20。
7. The complex surfactant of claim 5, wherein R is 1 Is C 6 -C 20 R is a hydrocarbon group of 2 Is H or C 1 -C 30 R is a hydrocarbon group of 3 Selected from H, -CH 3 or-CH 2 CH 3 ，x 1 +x 2 ＝0～20，y 1 +y 2 ＝1～20，z 1 +z 2 =0 to 10, and m is selected from any one of sodium ion, potassium ion, calcium ion, or magnesium ion.
8. A process for preparing a complex surfactant according to any one of claims 1 to 7, comprising the steps of:
step 1, using alkyl aniline as an initiator, reacting with an epoxy compound, and optionally carrying out end capping treatment after the reaction is finished to obtain alkyl aniline polyether;
step 2, carrying out sulfonation treatment on the alkyl aniline polyether to obtain the alkyl aniline polyether benzene sulfonate;
and 3, mixing the anionic surfactant, namely the alkyl aniline polyether benzene sulfonate and the cationic surfactant to obtain the composite surfactant.
9. The method of preparing according to claim 8, wherein the hydrocarbylaniline has the formula: r is R 1 -Ph-NH 2 Wherein Ph represents phenyl, R 1 The method of any one of claims 1-7.
10. Use of a complex surfactant according to any one of claims 1 to 7 for enhanced oil recovery.
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