CN104277814B - Surfactant oil displacement composition, preparation method and application - Google Patents
Surfactant oil displacement composition, preparation method and application Download PDFInfo
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- CN104277814B CN104277814B CN201310286400.9A CN201310286400A CN104277814B CN 104277814 B CN104277814 B CN 104277814B CN 201310286400 A CN201310286400 A CN 201310286400A CN 104277814 B CN104277814 B CN 104277814B
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 58
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 150000001412 amines Chemical group 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 85
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 150000002191 fatty alcohols Chemical class 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 44
- -1 polyoxypropylene Polymers 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000003153 chemical reaction reagent Substances 0.000 claims description 28
- 229920001451 polypropylene glycol Polymers 0.000 claims description 26
- 239000001294 propane Substances 0.000 claims description 22
- 238000006467 substitution reaction Methods 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 19
- 150000001450 anions Chemical class 0.000 abstract description 9
- 208000027418 Wounds and injury Diseases 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 6
- 208000014674 injury Diseases 0.000 abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 abstract description 6
- 239000003129 oil well Substances 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 153
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 76
- 239000012190 activator Substances 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 40
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 40
- 238000003756 stirring Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 150000001768 cations Chemical class 0.000 description 20
- 239000010779 crude oil Substances 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 20
- 239000000194 fatty acid Substances 0.000 description 20
- 229930195729 fatty acid Natural products 0.000 description 20
- 150000004665 fatty acids Chemical class 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000013517 stratification Methods 0.000 description 20
- 238000010792 warming Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 229920000570 polyether Polymers 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- JIRNEODMTPGRGV-UHFFFAOYSA-N pentadecylbenzene Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1 JIRNEODMTPGRGV-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011435 rock Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 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 5
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- JUPMBRMEHSUGLE-UHFFFAOYSA-N butenyl Chemical compound CCC=[CH] JUPMBRMEHSUGLE-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 4
- XDTYUYVIGLIFCW-UHFFFAOYSA-N 4-phenylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=CC=C1 XDTYUYVIGLIFCW-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 4
- 239000003027 oil sand Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GQFZYTXZJHSSEA-UHFFFAOYSA-M decyl(triethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CC)(CC)CC GQFZYTXZJHSSEA-UHFFFAOYSA-M 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229940057874 phenyl trimethicone Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229940045998 sodium isethionate Drugs 0.000 description 2
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- LINXHFKHZLOLEI-UHFFFAOYSA-N trimethyl-[phenyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 LINXHFKHZLOLEI-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 239000004575 stone Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to surfactant oil displacement composition, preparation method and application, mainly solve surfactant oil displacement efficiency during tertiary oil recovery poor, simultaneously because oil displacement system contains inorganic base, the problem of injury, etching apparatus and pipeline and difficult demulsification are brought to stratum and oil well.The present invention is by using surfactant oil displacement composition, including cationic surfactant and anion nonionic surfactant, the mol ratio of described cationic surfactant and anion nonionic surfactant is 1: 0.01~1: 100, its cationic surfactant is selected from least one of quaternary ammonium salt or quaternary amine alkali, anion nonionic surfactant general molecular formula is as follows, wherein M is the technical scheme of any one in alkali metal, alkaline-earth metal, ammonium root, the problem is preferably solved, during tertiary oil production in oil field：Or
Description
Technical field
The present invention relates to surfactant oil displacement composition, preparation method and its application in the displacement of reservoir oil of oil field.
Background technology
With the increase of world energy sources demand, the rational exploitation and utilization of oil has caused the very big attention of people, to oil
Yield and production efficiency requirement also more and more higher.The high-efficiency mining of petroleum resources is realized, for improving crude output not
Only there is realistic meaning, with more important strategic importance.Conventional oil production method（Primary and secondary method）Normally only produce former
The 1/3 of oily oil in place, the crude oil that there is also about 2/3 fails extraction, therefore in the case where energy day is becoming tight, improves tar productivity
The key subjects that oil exploitation is studied are turned into.Tertiary oil recovery technology is then a kind of effective method for improving tar productivity, can be divided
For four major classes：One is that heating power drives, including steam drive, combustion in situ etc.；Two be that mixed phase drives, including CO2Mixed phase, hydrocarbon mixed phase and other
Inert gas mixed phase drives；Three be chemical flooding；Four be microbe oil production, including biopolymer, MICROBIAL SURFACTANT are driven.Change
Learn that to drive be technology that is extremely important in intensified oil reduction and implementing on a large scale, including polymer flooding, surfactant flooding, caustic waterflooding etc.
And the multiple combinations technology of polymer, alkali, surfactant.The effect of chemical flooding is physical action and the knot of chemical action
Really, physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.Chemical action
Core is to reduce the interfacial tension of displacing fluid and crude oil.Surfactant is due to having oleophylic concurrently（It is hydrophobic）With it is hydrophilic（Oleophobic）Property
Matter, when surfactant is dissolved in water, molecule is mainly distributed on oil-water interfaces, can significantly reduce oil water interfacial tension.Oil
The reduction of water interfacial tension means that surfactant system can overcome the cohesive force between crude oil, and larger oil droplet is dispersed into small oil
Drop, so as to improve percent of pass when crude oil flows through pore throat.The oil displacement efficiency of surfactant, which is also manifested by, makes the rock table of oleophylic
Face wettability reversal, emulsification of crude oil, the raising effect such as surface charge density and oil droplet coalescence, this is surfactant in chemical flooding
The reason for playing very important in technology.
Current surface active agent for tertiary oil recovery uses Recompounded multielement system mostly, while including non-ionic surfactant
The auxiliary agents such as alkali and alcohol are additionally added in agent and ionic surfactant, part formulation.As patent CN101024764A provides one
The surfactant of oil-field thick-oil well is planted, the activating agent is by water, piece alkali, ethanol, oleic acid, APES, ten
Dialkyl benzene sulfonic acids sodium is constituted.For another example patent CN1458219A discloses a kind of surfactant polymer of tertiary oil recovery application
Pure binary ultralow interfacial tension combination flooding formula, wherein the surfactant used be petroleum sulfonate or using petroleum sulfonate as
Host adds the complexed surfactant of diluent and other surfactant compounds, and the percentage by weight of its component is mahogany acid
Salt 50~100%, alkylsulfonate 0~50%, carboxylate 0~50%, alkylaryl sulfonates 0~35%, low-carbon alcohols 0~20%.Again
Such as patent CN1394935 has invented a kind of chemical oil displacement agent, and it mainly includes sodium octylbenzene sulfonate anion surfactant, table
Face activity agent aid, surfactant synergist, surface active agent solubilization agent.This oil displacement agent can significantly reduce the knot of viscous crude
Structure viscosity, while oil water interfacial tension can be reduced, so as to improve oil recovery factor.
However, above-mentioned surface active agent for tertiary oil recovery still suffers from more problem, mainly surfactant activity is poor, drive
Oily efficiency is low, simultaneously because surfactant system is excessively complicated, thus Produced Liquid demulsification is difficult, and sewage disposal difficulty is big；Separately
It is outer that injury is brought to stratum and oil well because oil displacement system contains inorganic base, the problems such as causing etching apparatus and pipeline, and due to
Inorganic base can seriously reduce the viscosity of polymer, have to greatly improve the concentration of polymer for the viscosity needed for reaching, make
Oil recovery integrated cost is improved；The high temperature resistance of surfactant, high salt tolerance, anti-high salinity it is limited in one's ability.
It is well known that anion surfactant, such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate are at present
It is widely used in during tertiary oil recovery, and cationic surfactant easily adsorbs or produced precipitation because of it by stratum, therefore drop
The ability of low oil water interfacial tension, is generally not used for tertiary oil recovery.Because cationic and anionic surfactant is mixed close to equal proportion
Its aqueous solution easily forms precipitation during conjunction, matches somebody with somebody so as to cause cationic and anionic surfactant mixed system not only to turn into the application
5 taboos, and correlation theory research is also more delayed.Research discovery in recent years, cationic and anionic surfactant mixed system
The aqueous solution has many anomalous properties, such as because cationic and anionic surfactant has strong electrostatic interaction in aqueous
Interaction between hydrophobic carbon chain, promotes two kinds with the interionic association of different charged surfactants, in the solution
Micella is readily formed, the surface-active higher than single surfactant is produced.In addition, cationic and anionic surfactant is mixed
System can obviously reduce absorption loss of the cationic surfactant on rock core, so as to significantly reduce cation surface activating
The inherent shortcoming of agent.
Gong Yujun etc.（See 2 months 2000 the 1st phase Northwest University's journals (natural science edition) of volume 30,28~31）Research
Think cetyl trimethylammonium bromide（CTAB）With lauryl sodium sulfate（SDS）Mixed system has solubilization.In stone
In oily recovery process, using solubilization can " displacement of reservoir oil ", will stick under the oil wash on the sandstone of rock stratum, adopted so as to improve oil
Yield.Huang Hongdu etc.（See petroleum gas journal in August, 2007 volume 29 the 4th phase, 101~104）Have studied petroleum sulfonate,
The anion surfactants such as petroleum carboxylate, alkylbenzenesulfonate and cetyl trimethylammonium bromide, alkali compound system
Interfacial tension simultaneously draws to draw a conclusion：The addition of cationic surfactant makes petroleum carboxylate, alkylbenzenesulfonate, oil sulphur
The interfacial activity of hydrochlorate is improved.
The studies above result shows anions and canons Surfactant Mixing Systems for reduction oil water interfacial tension, raising
Oil displacement efficiency has certain effect.But the former result of study shows that its interface performance still has much room for improvement, and the latter is in system
Alkali is still employed, so that alkali can not be avoided to bring injury to stratum and oil well, etching apparatus and pipeline and demulsification difficulty etc. are asked
Topic.Other above-mentioned system is easier generation precipitation, is unfavorable for practical application.
Therefore, one aspect of the present invention, which absorbs, has used for reference forefathers on anions and canons Surfactants mixed system research knot
Really, traditional anion surfactant is on the other hand replaced using Anionic-nonionic surfactant, overcomes yin, yang
When ionic surface active agent is compounded easily the shortcomings of precipitate, invented for the displacement of reservoir oil cationic surfactant and it is cloudy from
Son-non-ionic surfactant composition.
The content of the invention
One of technical problems to be solved by the invention are existing surfactant oil displacement efficiencies during tertiary oil recovery
Difference, simultaneously because oil displacement system contains inorganic base, injury, etching apparatus and pipeline and the difficulty that is demulsified are brought to stratum and oil well
Problem is there is provided a kind of new surfactant oil displacement composition, and said composition has that interfacial activity is high, washing oil ability is strong, body
System is simple, will not bring injury to stratum and oil well, etching apparatus and pipeline and will not result in the advantage of demulsification difficulty.
The two of the technical problems to be solved by the invention are to provide a kind of surface corresponding with solving technical problem one and lived
The preparation method of property agent composition.
The three of the technical problems to be solved by the invention are one of technical problem surfactant oil displacement compositions
Application in the displacement of reservoir oil of oil field.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Surfactant oil displacement is combined
Thing, including cationic surfactant and Anionic-nonionic surfactant, described cationic surfactant with it is cloudy from
The mol ratio of son-nonionic surfactant is 1: 0.01~1: 100, and its cationic surfactant is selected from quaternary ammonium salt or season
At least one of amine base, Anionic-nonionic surfactant molecule formula is：
Or
Wherein M is any one in alkali metal, alkaline-earth metal, ammonium root；R is H, C1~C20Alkyl, C6~C10Aryl
Or any one in substituted aryl；R ' is C1~C10Alkylidene；M, n are any one integer in 1~10；X, y be 0~
Any one integer or decimal in 100, x, y are more preferably any one integer or decimal in 0~50；R is general molecular formula
Middle M and SO3Group or M and COO groups mol ratio, r=1 when M is alkali metal or ammonium root, when M is alkaline-earth metal r=
0.5。
Preferable x in above-mentioned technical proposal>0.
Cationic surfactant described in above-mentioned technical proposal preferably is selected from tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide
At least one of.Carbon number in the cationic surfactant molecule is preferably 4 ~ 40.The Anionic-nonionic
Surfactant cationic M preferably is selected from Na, K, Mg, Ca or NH4In any one.R is preferably H, C5~C15Alkyl, virtue
Base.R ' is preferably C1~C5Alkylidene.
The mol ratio of cationic surfactant described in above-mentioned technical proposal and Anionic-nonionic surfactant is excellent
It is 1: 0.1~1: 10 to select scheme.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One of above-mentioned technical problem correspondence
Technical scheme described in surfactant oil displacement composition preparation method, comprise the following steps：
A) unrighted acid, acidic catalyst and aromatic hydrocarbon are added into reactor, in 50~150oC addition reactions 1~
20 hours, wherein unrighted acid：Aromatic hydrocarbons mol ratio is 1：(0.5~1.0)；After reaction terminates, in temperature 100 ~ 300oC,
10 ~ 100kg/cm of pressure2Hydrogenation reaction 1 ~ 10 hour, so that aryl acquirement carboxylic acid is reduced into aryl substituted alcohols；Aryl is taken
Reactor is added for alcohol, base catalyst and required expoxy propane, oxirane, in 100~200oC carries out etherification reaction 1
~20 hours；Then add sulfonated reagent or carboxylating reagent carries out sulfonation/carboxylation reaction, in 50~100oC reactions 1~20 are small
When, wherein aryl replaces fatty alcohol polyoxypropylene APEO：The mol ratio of sulfonated reagent/carboxylating reagent is 1：(1~4)；
After reaction terminates, acidic aqueous solution is used（For example aqueous hydrochloric acid solution, aqueous sulfuric acid, phosphate aqueous solution, sodium bisulphate solution or
Person's aqueous potassium hydrogen sulfate）Regulation carries out water-oil separating to pH=1 ~ 3, and oil phase adds alkali lye and is neutralized to pH=7 ~ 9, obtains aryl
Replace fatty alcohol polyoxypropylene polyethenoxy ether sulphonate or aryl substitution fatty alcohol polyoxypropylene polyethenoxy ether carboxylate cloudy
Ion-nonionic surfactant；
B) the Anionic-nonionic surfactant difference obtained by cationic surfactant and according to step a) is molten
It is then well mixed according to mol ratio 1: 0.1~1: 10 in Xie Yushui.
In above-mentioned technical proposal, step a) the base catalyst preferred schemes are selected from least one of NaOH or KOH.
In above-mentioned technical proposal, hydrogenation reaction is reaction well known in the art, and it is anti-to promote generally to use hydrogenation catalyst
Should, conventional hydrogenation catalyst has Pd/C catalyst, Pt/C catalyst, Raney's nickel catalyst etc..Pd/C or Pt/C catalyst is expensive
Tenor is not the key of the present invention, and such as Pd or Pt contents can be 0.5~5wt%.The Pd or Pt used in embodiment contains
Measure as 0.5wt%.
In order to solve the above-mentioned technical problem three, technical scheme is as follows：One of above-mentioned technical problem is corresponding
Application of the surfactant oil displacement composition in the displacement of reservoir oil of oil field described in any one technical scheme.
The surfactant oil displacement composition of the present invention is on the one hand due to anions and canons surfactant opposite charges pole
Property base between strong electrostatic attraction effect so that surfactant molecule increases in adsorbed on interfaces amount, critical micelle concentration
Significantly reduce, so that with the incomparable high surface of single surfactant；Simultaneously because surface activator composition
The interfacial activity of superelevation, its aqueous solution, so as to effectively overcome the cohesive force between crude oil, can have with crude oil formation ultralow interfacial tension
Beneficial to the outflow of crude oil, and then greatly improve oil displacement efficiency.Another aspect surface activator composition can change oil reservoir surface
Wetability, the cationic surfactant in such as composition is mutual by the electronegative group with absorption on a solid surface
Effect, is desorbed it, glossy wet structure is changed into neutral wetting or water wetting surface, reduction crude oil is in the surface of solids
Adhesion work, so as to be conducive to the stripping of crude oil.Anions and canons surfactant mixed solution there is solubilising to make crude oil simultaneously
With, further the crude oil sticked on the sandstone of rock stratum can be washed down, improve oil recovery factor.
Surface activator composition of the present invention is used during tertiary oil recovery, it is high with interfacial activity：Live on compound surface
Property agent composition consumption be to remain to and underground crude oil formation 10 under the conditions of 0.01~0.05wt%-3~10-4MN/m ultralow boundary
Face tension force；Washing oil ability is strong：Surface activator composition is to the washing oil rate of crude oil more than 40%；Surface activator composition system
Simply.Because system is free of inorganic base, thus inorganic base is caused to stratum when avoiding field application injury, equipment is caused
Corrosion and the problem of thus caused demulsification is difficult, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1a】
By CH3(CH2)10CH=CHCOOH, pentadecyl benzene and perchloric acid add reactor, are passed through N2It is 35kg/ to pressure
cm2, in 200oC reacts 2 hours, wherein CH3(CH2)10CH=CHCOOH：Pentadecyl benzene：Perchloric acid mol ratio is 1：1：0.1.
After reaction terminates, the Pd/C catalyst of fatty acid wt 1% is added, 100oC、100kg/cm2Pressure hydrogenation reaction 10 hours, and
Pd/C catalyst is filtered out afterwards；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio 1：1.5 add
Reactor, stirring adds required expoxy propane after 30 minutes, in 150oC reacts 5 hours；Then add the desired amount of epoxy second
Alkane, in 200oC reacts 1 hour, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：
ClCH2SO3Na mol ratios 1：3 add sulfonated reagent, are warming up to 70oC reacts 10 hours.It is water-soluble with 5wt% hydrochloric acid after reaction terminates
It is 2.5 that liquid, which is neutralized to pH value, and stratification, oil phase is neutralized to pH value 8 with 2 wt %NaOH, and vacuum removal moisture obtains target
Product anions-nonionic surfactant.
Anionic-nonionic surfactant prepared by etamon chloride and the present invention is dissolved in water, and is stirred
Mix 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic surface
Activating agent mol ratio 1: 0.1 is well mixed, and obtains a of surface activator composition 1, and it is constituted, structure is shown in Table 1 a.
【Embodiment 2a】
By CH3(CH2)6CH=CHCOOH, octyl group benzene and ClSO3H adds reactor, is passed through N2It is 100kg/cm to pressure2,
In 50oC reacts 20 hours, wherein CH3(CH2)6CH=CHCOOH：Octyl group benzene：ClSO3H mol ratios are 1：1：0.25.Reaction terminates
Afterwards, the Pd/C catalyst of fatty acid wt 0.2% is added, 120oC、120kg/cm2Pressure hydrogenation reaction 8 hours, is then filtered out
Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：1.5 add reactor, stir
Mix and required expoxy propane is added after 30 minutes, in 120oC reacts 7 hours；The desired amount of oxirane is then added, in 160oC
Reaction 4 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：Sodium isethionate mole
Than 1：2.5 add sulfonated reagent, are warming up to 90oC reacts 8 hours.After reaction terminates, pH value is neutralized to 5wt% aqueous hydrochloric acid solutions
For 2.5, stratification, oil phase is neutralized to pH value 8 with 10wt % ammoniacal liquor, vacuum removal moisture, obtains target product anion-non-
Ionic surface active agent.
Anionic-nonionic surfactant prepared by hexadecyltrimethylammonium chloride and the present invention is dissolved separately in
In water, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-
Ionic surface active agent mol ratio 1: 0.5 is well mixed, and obtains a of surface activator composition 2, and it is constituted, structure is shown in Table 1 a.
【Embodiment 3a】
By CH3(CH2)4CH=CH(CH2)3COOH, amylbenzene and p-methyl benzenesulfonic acid add reactor, are passed through N2To pressure
For 100kg/cm2, in 50oC reacts 20 hours, wherein CH3(CH2)4CH=CH(CH2)3COOH：Amylbenzene：Toluene sulfonic acide mole
Than for 1：1：0.25.After reaction terminates, the Pt/C catalyst of fatty acid wt 0.2% is added, 300oC、100kg/cm2Pressure adds
Hydrogen reacts 1 hour, then filters out Pt/C catalyst；The aryl that abovementioned steps are obtained replace fatty alcohol and CsOH according to mole
Than 1：1.5 add reactor, and stirring adds required expoxy propane after 30 minutes, in 100oC reacts 20 hours；Then add institute
The oxirane of requirement, in 200oC reacts 1 hour, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to
Polyethers：Hydroxyl amyl group sodium sulfonate mol ratio 1：4 add sulfonated reagent, are warming up to 50oC reacts 20 hours.After reaction terminates, 5wt% is used
Aqueous hydrochloric acid solution is neutralized to pH value for 2.5, stratification, and oil phase is neutralized to pH value 8 with 5 wt %NaOH, vacuum removal moisture,
Obtain target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by phenyl trimethicone ammonium chloride and the present invention is dissolved separately in water
In, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 1.5 is well mixed, and obtains a of surface activator composition 3, and it is constituted, structure is shown in Table 1 a.
【Embodiment 4a】
By CH3CH2CH=CH(CH2)8COOH, p- ethvl-biphenyl and perchloric acid add reactor, are passed through N2It is to pressure
80kg/cm2, in 150oC reacts 1 hour, wherein CH3CH2CH=CH(CH2)8COOH：P- ethvl-biphenyl：Perchloric acid mol ratio is
1：1：0.10.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 100oC、10kg/cm2Pressure hydrogenation is anti-
Answer 10 hours, then filter out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：
1.5 add reactor, and stirring adds required expoxy propane after 30 minutes, in 140oC reacts 10 hours；Then add aequum
Oxirane, in 180oC reacts 3 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：Hydroxypropyl azochlorosulfonate acid sodium mol ratio 1：2 add sulfonated reagent, are warming up to 70oC reacts 8 hours.After reaction terminates, 5wt% salt is used
It is 2.5 that aqueous acid, which is neutralized to pH value, and stratification, oil phase is neutralized to pH value 7 with 2 wt %KOH, and vacuum removal moisture is obtained
Target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant difference prepared by stearyl dimethyl benzyl ammonium chloride and the present invention is molten
In Xie Yushui, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：It is cloudy from
Son-nonionic surfactant mol ratio 1: 10 is well mixed, and obtains a of surface activator composition 4, and it is constituted, structure is shown in Table
1 a。
【Embodiment 5a】
By CH3 CH2CH=CH(CH2)7COOH, benzene and perchloric acid add reactor, are passed through N2It is 40kg/cm to pressure2, in
120oC reacts 5 hours, wherein CH3 CH2CH=CH(CH2)7COOH：Benzene：Perchloric acid mol ratio is 1：1：0.12.After reaction terminates,
The Pd/C catalyst of fatty acid wt 0.2% is added, 150oC、30kg/cm2Pressure hydrogenation reaction 8 hours, then filters out Pd/C
Catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio 1：2 add reactor, stir 30 points
Required expoxy propane is added after clock, in 150oC reacts 5 hours；The desired amount of oxirane is then added, in 150oC reactions 8
Hour, obtain aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：Hydroxyl butyl sulfonic acid sodium mol ratio 1：2
Sulfonated reagent is added, 70 are warming up tooC reacts 8 hours.After reaction terminates, it is 2.5 that pH value is neutralized to 5wt% aqueous hydrochloric acid solutions,
Stratification, oil phase is with 10wt%Mg (OH)2The aqueous solution is neutralized to pH value 8, vacuum removal moisture, obtain target product anion-
Nonionic surfactant.
Anionic-nonionic surfactant prepared by decyl triethylammonium hydroxide and the present invention is dissolved separately in water
In, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 1.3 is well mixed, and obtains a of surface activator composition 5, and it is constituted, structure is shown in Table 1 a.
【Embodiment 6a】
By CH3(CH2)3CH=CHCH2COOH, 4- phenyl-benzene sulfonic acid and perchloric acid add reactor, are passed through N2It is to pressure
50kg/cm2, in 140oC reacts 3 hours, wherein CH3(CH2)3CH=CHCH2COOH：4- phenyl-benzene sulfonic acid：Perchloric acid mol ratio
For 1：1：0.15.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 200oC、50kg/cm2Pressure is hydrogenated with
Reaction 6 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio
1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 150oC reacts 5 hours；Then add aequum
Oxirane, in 150oC reacts 8 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：ClCH2SO3Na mol ratios 1：2 add sulfonated reagent, are warming up to 85oC reacts 5 hours.After reaction terminates, 5wt% hydrochloric acid waters are used
Solution is neutralized to pH value for 2.5, stratification, and oil phase is with 10 wt%Ca (OH)2Aqueous suspension be neutralized to pH value 8, vacuum takes off
Moisture removal, obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by DTAC and the present invention is dissolved separately in
In water, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-
Ionic surface active agent mol ratio 1: 6 is well mixed, and obtains a of surface activator composition 6, and it is constituted, structure is shown in Table 1 a.
【Embodiment 7a】
By CH3(CH2)4CH=CH(CH2)3COOH, biphenyl and p-methyl benzenesulfonic acid add reactor, are passed through N2It is to pressure
50kg/cm2, in 100oC reacts 5 hours, wherein CH3(CH2)4CH=CH(CH2)3COOH：Biphenyl：P-methyl benzenesulfonic acid mol ratio
For 1：1：0.15.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 160oC、40kg/cm2Pressure is hydrogenated with
Reaction 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio
1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 120oC reacts 8 hours；Then add aequum
Oxirane, in 150oC reacts 6 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：Sodium chloroacetate：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.After reaction terminates,
It is neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid solutions, stratification, oil phase is with 10 wt%Mg (OH)2Aqueous suspension be neutralized to pH
Value 8, vacuum removal moisture obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by tetrabutylammonium chloride and the present invention is dissolved in water, and is stirred
Mix 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 2 is well mixed, and obtains a of surface activator composition 7, and it is constituted, structure is shown in Table 1 a.
【Embodiment 8a】
By CH3CH=CHCOOH, 4- phenyl-benzene sulfonic acid and to perchloric acid add reactor, be passed through N2It is 50kg/ to pressure
cm2, in 130oC reacts 6 hours, wherein CH3CH=CHCOOH：4- phenyl-benzene sulfonic acid：Perchloric acid mol ratio is 1：1：0.10.Instead
After should terminating, the Pd/C catalyst of fatty acid wt 0.2% is added, 160oC、40kg/cm2Pressure hydrogenation reaction 8 hours, then
Filter out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：2 add reactor,
Stirring adds required expoxy propane after 30 minutes, in 120oC reacts 8 hours；The desired amount of oxirane is then added, in
150oC reacts 6 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：3- chloropropionic acid sodium：
NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.After reaction terminates, 5wt% hydrochloric acid waters are used
Solution is neutralized to pH value 2.5, stratification, and oil phase is with 10 wt%Ca (OH)2Aqueous suspension be neutralized to pH value 8, vacuum removal
Moisture, obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by dioctadecyl dimethyl ammonium chloride and the present invention dissolves respectively
Yu Shuizhong, stirs 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-
Nonionic surfactant mol ratio 1: 4 is well mixed, and obtains a of surface activator composition 8, and it is constituted, structure is shown in Table 1 a.
【Embodiment 9a】
By CH3(CH2)4CH=CH(CH2)2COOH, p- phenyl-benzoic acid and p-methyl benzenesulfonic acid add reactor, are passed through
N2It is 50kg/cm to pressure2, in 120oC reacts 5 hours, wherein CH3(CH2)4CH=CH(CH2)2COOH：P- phenyl-benzoic acid：
P-methyl benzenesulfonic acid mol ratio is 1：1：0.20.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added,
170oC、40kg/cm2Pressure hydrogenation reaction 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fat
Fat alcohol and KOH are according to mol ratio 1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 140oC reacts
8 hours；The desired amount of oxirane is then added, in 150oC reacts 7 hours, obtains aryl substitution fatty alcohol polyoxypropylene and gathers
Oxygen vinethene；Then according to polyethers：Sodium chloroacetate：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts
10 hours.After reaction terminates, pH value 2.5 is neutralized to 5wt% aqueous hydrochloric acid solutions, stratification, oil phase is with 10 wt% NaOH
With to pH value 8, vacuum removal moisture obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by four octyl group ammonium chlorides and the present invention is dissolved in water, and is stirred
Mix 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 8 is well mixed, and obtains a of surface activator composition 9, and it is constituted, structure is shown in Table 1 a.
【Embodiment 10a】
By CH3(CH2)4CH=CH(CH2)3COOH, nonyl benzene and p-methyl benzenesulfonic acid add reactor, are passed through N2To pressure
For 50kg/cm2, in 160oC reacts 8 hours, its CH3(CH2)4CH=CH(CH2)3COOH：Nonyl benzene：P-methyl benzenesulfonic acid mole
Than for 1：1：0.15.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 170oC、60kg/cm2Pressure adds
Hydrogen reacts 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replace fatty alcohol and NaOH according to mole
Than 1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 160oC reacts 8 hours；Needed for then adding
The oxirane of amount, in 150oC reacts 8 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：3- chloropropionic acid sodium：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.Reaction terminates
Afterwards, pH value 2.5, stratification are neutralized to 5wt% aqueous hydrochloric acid solutions, oil phase is neutralized to pH value 8 with 10 wt% NaOH, and vacuum takes off
Moisture removal, obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by benzyltriethylammoinium chloride and the present invention is dissolved separately in water
In, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 1.5 is well mixed, and obtains a of surface activator composition 10, and it is constituted, structure is shown in Table 1 a.
【Embodiment 11a】
0.30wt% surface activator compositions prepared by embodiment 5a and 0.15wt% polyacrylamides (molecular weight 2600
Ten thousand) aqueous solution is well mixed, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1a surfactant oil displacements composition is constituted and structure
【Embodiment 12a】Surfactant interface performance test
Surfactant oil displacement composition and Shuanghe Oil Field are determined with TX-500C rotating interfacial tensimeters5-
11 series of strata oil water interfacial tensions.It is 81 to determine temperatureoC, stratum water is NaHCO3Type, salinity is 7947mg/L, chloride ion content
2002 mg/L, Ca2+Content 20 mg/L, Mg2+The mg/L of content 12.2, surface activator composition consumption is 0.3 wt %.
Table 2a surfactant oil displacements composition and Shuan He oil fields5-11 series of strata oil water interfacial tension results
| Embodiment | Interfacial tension (mN/m) |
| 1 a | 0.0088 |
| 2 a | 0.0081 |
| 3 a | 0.0047 |
| 4 a | 0.0085 |
| 5 a | 0.0002 |
| 6 a | 0.0068 |
| 7 a | 0.0015 |
| 8 a | 0.0058 |
| 9 a | 0.0004 |
| 10 a | 0.0005 |
| 11 a | 0.0032 |
From a of table 2, compound surfactant prepared by a of a of embodiment 1~10 has good for Henan Oil Field
Interface performance.The a of embodiment 11 shows that after surfactant prepared by the present invention is compounded with polymer, its interface performance is still
Well.
The embodiment 10a surface activator compositions prepared are configured to various concentrations, respectively test and Shuanghe in Henan's oil
Field5-11 series of strata oil water interfacial tensions, the results are shown in Table 3 a.
The a of table 3a various concentrations surface activator composition 10 and Shuanghe Oil Field5-11 series of strata oil water interfacial tensions
| Dosage of surfactant (%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.008 | 0.006 | 0.004 | 0.001 | 0.0008 | 0.0005 |
The above results show that surfactant oil displacement composition of the present invention has very high boundary for Henan Oil Field crude oil
Face activity.
The surface activator composition of a of embodiment 5 preparations is determined again with TX-500C rotating interfacial tensimeters with
The former factory's oil water interfacial tension of oil extraction in oil field three.It is 80 to determine temperatureoC, formation water salinity is 79439mg/L, Ca2+Content 592
Mg/L, Mg2+Content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.004mN/m, shows this
The surfactant of invention still has well interface characteristics not only for low mineralization oil reservoir simultaneously for high temperature and high salt oil deposit
Can, have the advantages that the scope of application is wide.
【Embodiment 13a】Surface activator composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sands, according to oil：Sand=1：4 (weight ratios) are 81oC agings 7 days, every 2 is small
When stir 5 minutes；The oil-sand 5g after above-mentioned aging is then taken out, oil-sand is pressed with 0.3 wt % surfactant solution：Solution=
1：10（Weight ratio）It is well mixed, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, use 50ml
Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Utilize standard curve gauging surface activator solution Central Plains
Oil concentration.
Table 4a surfactant washing oil results
【The a of embodiment 14】Surface activator composition Oil Displacing Capacity is studied
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns2Rock core on carry out oil displacement test.First
Use Shuanghe Oil Field5-11 series of strata stratum water drive is to oil-free, metaideophone 0.3PV (rock pore volume) surfactant group
After compound, then water drive to oil-free is produced, and is improved oil recovery factor and be the results are shown in Table 5 a.
Table 5a surface activator composition oil displacement test results
| Embodiment | Improve recovery ratio % |
| 1 a | 7.7 |
| 2 a | 6.5 |
| 3 a | 6.1 |
| 4 a | 5.8 |
| 5 a | 7.1 |
| 6 a | 6.3 |
| 7 a | 6.0 |
| 8 a | 6.7 |
| 9 a | 7.0 |
| 10 a | 6.8 |
【The a of comparative example 1】
According to Northwest University's journal (natural science edition) 2000 year 2 month the 1st phase of volume 30, the method such as 28~31 Gong Yu armies
Cetyl trimethylammonium bromide (CTAB) and lauryl sodium sulfate (SDS) are configured to mixed system (mol ratio 1：1.5),
It is tested respectively in 0.3 wt % consumptions and Shuanghe Oil Field5-11 series of strata crude oil oil water interfacial tension, washing oil rate and drive
Oiliness energy, it is as a result as follows：
Table 6a reference oil displacement agent performances
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.03 | 45.6 | 2.8 |
【The a of comparative example 2】
According to petroleum gas journal in August, 2007 the 4th phase of volume 29, (101~104) method such as Huang Hong degree etc. is by 0.01
Wt % cetyl trimethylammonium bromides and 0.02 wt % anion surfactants petroleum sulfonates and 1.8 wt %Na2CO3
Mixed system is configured to, it is tested respectively in 0.3 wt % consumptions and Shuanghe Oil Field5-11 series of strata crude oil oil-water interfaces
Tension force, washing oil rate and Oil Displacing Capacity, it is as a result as follows：
Table 7a reference oil displacement agent performances
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.008 | 56.3 | 4.2 |
【Embodiment 1b】
By CH3(CH2)10CH=CHCOOH, pentadecyl benzene and perchloric acid add reactor, are passed through N2It is 35kg/ to pressure
cm2, in 200oC reacts 2 hours, wherein CH3(CH2)10CH=CHCOOH：Pentadecyl benzene：Perchloric acid mol ratio is 1：1：0.1.
After reaction terminates, the Pd/C catalyst of fatty acid wt 1% is added, 100oC、100kg/cm2Pressure hydrogenation reaction 10 hours, and
Pd/C catalyst is filtered out afterwards；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio 1：1.5 add
Reactor, stirring adds required expoxy propane after 30 minutes, in 150oC reacts 5 hours；Then add the desired amount of epoxy second
Alkane, in 200oC reacts 1 hour, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：
ClCH2SO3Na mol ratios 1：3 add sulfonated reagent, are warming up to 70oC reacts 10 hours.It is water-soluble with 5wt% hydrochloric acid after reaction terminates
It is 2.5 that liquid, which is neutralized to pH value, and stratification, oil phase is neutralized to pH value 8 with 2 wt %NaOH, and vacuum removal moisture obtains target
Product anions-nonionic surfactant.
Anionic-nonionic surfactant prepared by etamon chloride and the present invention is dissolved in water, and is stirred
Mix 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic surface
Activating agent mol ratio 1: 0.1 is well mixed, and obtains the b of surface activator composition 1, and it is constituted, structure is shown in Table 1 b.
【Embodiment 2b】
By CH3(CH2)6CH=CHCOOH, octyl group benzene and ClSO3H adds reactor, is passed through N2It is 100kg/cm to pressure2,
In 50oC reacts 20 hours, wherein CH3(CH2)6CH=CHCOOH：Octyl group benzene：ClSO3H mol ratios are 1：1：0.25.Reaction terminates
Afterwards, the Pd/C catalyst of fatty acid wt 0.2% is added, 120oC、120kg/cm2Pressure hydrogenation reaction 8 hours, is then filtered out
Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：1.5 add reactor, stir
Mix and required expoxy propane is added after 30 minutes, in 120oC reacts 7 hours；The desired amount of oxirane is then added, in 160oC
Reaction 4 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：Sodium isethionate mole
Than 1：2.5 add sulfonated reagent, are warming up to 90oC reacts 8 hours.After reaction terminates, pH value is neutralized to 5wt% aqueous hydrochloric acid solutions
For 2.5, stratification, oil phase is neutralized to pH value 8 with 10wt % ammoniacal liquor, vacuum removal moisture, obtains target product anion-non-
Ionic surface active agent.
Anionic-nonionic surfactant prepared by hexadecyltrimethylammonium chloride and the present invention is dissolved separately in
In water, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-
Ionic surface active agent mol ratio 1: 0.5 is well mixed, and obtains the b of surface activator composition 2, and it is constituted, structure is shown in Table 1 b.
【Embodiment 3b】
By CH3(CH2)4CH=CH(CH2)3COOH, amylbenzene and p-methyl benzenesulfonic acid add reactor, are passed through N2To pressure
For 100kg/cm2, in 50oC reacts 20 hours, wherein CH3(CH2)4CH=CH(CH2)3COOH：Amylbenzene：Toluene sulfonic acide mole
Than for 1：1：0.25.After reaction terminates, the Pt/C catalyst of fatty acid wt 0.2% is added, 300oC、100kg/cm2Pressure adds
Hydrogen reacts 1 hour, then filters out Pt/C catalyst；The aryl that abovementioned steps are obtained replace fatty alcohol and CsOH according to mole
Than 1：1.5 add reactor, and stirring adds required expoxy propane after 30 minutes, in 100oC reacts 20 hours；Then add institute
The oxirane of requirement, in 200oC reacts 1 hour, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to
Polyethers：Hydroxyl amyl group sodium sulfonate mol ratio 1：4 add sulfonated reagent, are warming up to 50oC reacts 20 hours.After reaction terminates, 5wt% is used
Aqueous hydrochloric acid solution is neutralized to pH value for 2.5, stratification, and oil phase is neutralized to pH value 8 with 5 wt %NaOH, vacuum removal moisture,
Obtain target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by phenyl trimethicone ammonium chloride and the present invention is dissolved separately in water
In, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 1.5 is well mixed, and obtains the b of surface activator composition 3, and it is constituted, structure is shown in Table 1 b.
【Embodiment 4b】
By CH3CH2CH=CH(CH2)8COOH, benzoic acid and perchloric acid add reactor, are passed through N2It is 80kg/ to pressure
cm2, in 150oC reacts 1 hour, wherein CH3CH2CH=CH(CH2)8COOH：Benzoic acid：Perchloric acid mol ratio is 1：1：0.10.Instead
After should terminating, the Pd/C catalyst of fatty acid wt 0.2% is added, 100oC、10kg/cm2Pressure hydrogenation reaction 10 hours, and
After filter out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：1.5 add reaction
Kettle, stirring adds required expoxy propane after 30 minutes, in 140oC reacts 10 hours；The desired amount of oxirane is then added,
In 180oC reacts 3 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：Hydroxypropyl sulfonic acid
Sodium mol ratio 1：2 add sulfonated reagent, are warming up to 70oC reacts 8 hours.After reaction terminates, it is neutralized to 5wt% aqueous hydrochloric acid solutions
PH value is 2.5, stratification, and oil phase is neutralized to pH value 7 with 2 wt %KOH, vacuum removal moisture, obtain target product it is cloudy from
Son-nonionic surfactant.
Anionic-nonionic surfactant difference prepared by stearyl dimethyl benzyl ammonium chloride and the present invention is molten
In Xie Yushui, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：It is cloudy from
Son-nonionic surfactant mol ratio 1: 10 is well mixed, and obtains the b of surface activator composition 4, and it is constituted, structure is shown in Table
1 b。
【Embodiment 5b】
By CH3CH2CH=CH(CH2)7COOH, benzene and perchloric acid add reactor, are passed through N2It is 40kg/cm to pressure2, in
120oC reacts 5 hours, wherein CH3 CH2CH=CH(CH2)7COOH：Benzene：Perchloric acid mol ratio is 1：1：0.12.After reaction terminates,
The Pd/C catalyst of fatty acid wt 0.2% is added, 150oC、30kg/cm2Pressure hydrogenation reaction 8 hours, then filters out Pd/C
Catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio 1：2 add reactor, stir 30 points
Required expoxy propane is added after clock, in 150oC reacts 5 hours；The desired amount of oxirane is then added, in 150oC reactions 8
Hour, obtain aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：Hydroxyl butyl sulfonic acid sodium mol ratio 1：2
Sulfonated reagent is added, 70 are warming up tooC reacts 8 hours.After reaction terminates, it is 2.5 that pH value is neutralized to 5wt% aqueous hydrochloric acid solutions,
Stratification, oil phase is with 10wt%Mg (OH)2The aqueous solution is neutralized to pH value 8, vacuum removal moisture, obtain target product anion-
Nonionic surfactant.
Anionic-nonionic surfactant prepared by decyl triethylammonium hydroxide and the present invention is dissolved separately in water
In, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-from
Sub- surfactant molar ratio 1: 1.3 is well mixed, and obtains the b of surface activator composition 5, and it is constituted, structure is shown in Table 1 b.
【Embodiment 6b】
By CH3(CH2)3CH=CHCH2COOH, benzene sulfonic acid and perchloric acid add reactor, are passed through N2It is 50kg/ to pressure
cm2, in 140oC reacts 3 hours, wherein CH3(CH2)3CH=CHCH2COOH：Benzene sulfonic acid：Perchloric acid mol ratio is 1：1：0.15.Instead
After should terminating, the Pd/C catalyst of fatty acid wt 0.2% is added, 200oC、50kg/cm2Pressure hydrogenation reaction 6 hours, then
Filter out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and NaOH according to mol ratio 1：2 add reactor,
Stirring adds required expoxy propane after 30 minutes, in 150oC reacts 5 hours；The desired amount of oxirane is then added, in
150oC reacts 8 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：ClCH2SO3Na rubs
You compare 1：2 add sulfonated reagent, are warming up to 85oC reacts 5 hours.After reaction terminates, pH value is neutralized to 5wt% aqueous hydrochloric acid solutions
For 2.5, stratification, oil phase is with 10 wt%Ca (OH)2Aqueous suspension be neutralized to pH value 8, vacuum removal moisture obtains target
Product anions-nonionic surfactant.
Anionic-nonionic surfactant prepared by DTAC and the present invention is dissolved separately in
In water, stir 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-non-
Ionic surface active agent mol ratio 1: 6 is well mixed, and obtains the b of surface activator composition 6, and it is constituted, structure is shown in Table 1 b.
【Embodiment 7b】
By CH3(CH2)4CH=CH(CH2)3COOH, biphenyl and p-methyl benzenesulfonic acid add reactor, are passed through N2It is to pressure
50kg/cm2, in 100oC reacts 5 hours, wherein CH3(CH2)4CH=CH(CH2)3COOH：Biphenyl：P-methyl benzenesulfonic acid mol ratio
For 1：1：0.15.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 160oC、40kg/cm2Pressure is hydrogenated with
Reaction 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio
1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 120oC reacts 8 hours；Then add aequum
Oxirane, in 150oC reacts 6 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：Sodium chloroacetate：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.After reaction terminates,
It is neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid solutions, stratification, oil phase is with 10 wt%Mg (OH)2Aqueous suspension be neutralized to pH
Value 8, vacuum removal moisture obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by tetrabutylammonium chloride and the present invention is dissolved in water, and is stirred
Mix 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 2 is well mixed, and obtains the b of surface activator composition 7, and it is constituted, structure is shown in Table 1 b.
【Embodiment 8b】
By CH3CH=CHCOOH, benzene sulfonic acid and to perchloric acid add reactor, be passed through N2It is 50kg/cm to pressure2, in
130oC reacts 6 hours, wherein CH3CH=CHCOOH：Benzene sulfonic acid：Perchloric acid mol ratio is 1：1：0.10.After reaction terminates, add
The Pd/C catalyst of fatty acid wt 0.2%, 160oC、40kg/cm2Pressure hydrogenation reaction 8 hours, then filters out Pd/C catalysis
Agent；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to mol ratio 1：2 add reactor, after stirring 30 minutes
Expoxy propane needed for adding, in 120oC reacts 8 hours；The desired amount of oxirane is then added, in 150oC reacts 6 hours,
Obtain aryl substitution fatty alcohol polyoxypropylene APEO；Then according to polyethers：3- chloropropionic acid sodium：NaOH mol ratios 1：1.5：
2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.After reaction terminates, pH value is neutralized to 5wt% aqueous hydrochloric acid solutions
2.5, stratification, oil phase is neutralized to pH value 8 with the 10 wt%NaOH aqueous solution, and vacuum removal moisture obtains target product cloudy
Ion-nonionic surfactant.
Anionic-nonionic surfactant prepared by dioctadecyl dimethyl ammonium chloride and the present invention dissolves respectively
Yu Shuizhong, stirs 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anion-
Nonionic surfactant mol ratio 1: 4 is well mixed, and obtains the b of surface activator composition 8, and it is constituted, structure is shown in Table 1 b.
【Embodiment 9b】
By CH3(CH2)4CH=CH(CH2)2COOH, benzoic acid and p-methyl benzenesulfonic acid add reactor, are passed through N2To pressure
For 50kg/cm2, in 120oC reacts 5 hours, wherein CH3(CH2)4CH=CH(CH2)2COOH：Benzoic acid：P-methyl benzenesulfonic acid rubs
You are than being 1：1：0.20.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 170oC、40kg/cm2Pressure
Hydrogenation reaction 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replaces fatty alcohol and KOH according to rubbing
You compare 1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 140oC reacts 8 hours；Then add institute
The oxirane of requirement, in 150oC reacts 7 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to
Polyethers：Sodium chloroacetate：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.Reaction terminates
Afterwards, pH value 2.5, stratification are neutralized to 5wt% aqueous hydrochloric acid solutions, oil phase is neutralized to pH value 8 with 10 wt% NaOH, and vacuum takes off
Moisture removal, obtains target product Anionic-nonionic surfactant.
Anionic-nonionic surfactant prepared by four octyl group ammonium chlorides and the present invention is dissolved in water, and is stirred
Mix 30 minutes, the 0.3 wt % aqueous solution is configured to, then by above-mentioned surfactant according to cation：Anionic-nonionic table
Face activating agent mol ratio 1: 8 is well mixed, and obtains the b of surface activator composition 9, and it is constituted, structure is shown in Table 1 b.
【Embodiment 10b】
By CH3(CH2)4CH=CH(CH2)3COOH, nonyl benzene and p-methyl benzenesulfonic acid add reactor, are passed through N2To pressure
For 50kg/cm2, in 160oC reacts 8 hours, its CH3(CH2)4CH=CH(CH2)3COOH：Nonyl benzene：P-methyl benzenesulfonic acid mole
Than for 1：1：0.15.After reaction terminates, the Pd/C catalyst of fatty acid wt 0.2% is added, 170oC、60kg/cm2Pressure adds
Hydrogen reacts 8 hours, then filters out Pd/C catalyst；The aryl that abovementioned steps are obtained replace fatty alcohol and NaOH according to mole
Than 1：2 add reactor, and stirring adds required expoxy propane after 30 minutes, in 160oC reacts 8 hours；Needed for then adding
The oxirane of amount, in 150oC reacts 8 hours, obtains aryl substitution fatty alcohol polyoxypropylene APEO；Then according to poly-
Ether：3- chloropropionic acid sodium：NaOH mol ratios 1：1.5：2.0 add carboxylating reagent, are warming up to 75oC reacts 10 hours.Reaction terminates
Afterwards, pH value 2.5, stratification are neutralized to 5wt% aqueous hydrochloric acid solutions, oil phase is neutralized to pH value 8 with 10 wt% NaOH, and vacuum takes off
Moisture removal, obtains target product Anionic-nonionic surfactant.
【Embodiment 11b】
0.30wt% surface activator compositions prepared by the b of embodiment 5 and 0.15wt% polyacrylamide (molecular weight
2600 ten thousand) aqueous solution be well mixed, obtain a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1b surfactant oil displacements composition is constituted and structure
【The b of embodiment 12】Surfactant interface performance test
Surfactant oil displacement composition and Shuanghe Oil Field are determined with TX-500C rotating interfacial tensimeters5-
11 series of strata oil water interfacial tensions.It is 81 to determine temperatureoC, stratum water is NaHCO3Type, salinity is 7947mg/L, chloride ion content
2002 mg/L, Ca2+Content 20 mg/L, Mg2+The mg/L of content 12.2, surface activator composition consumption is 0.3 wt %.
Table 2b surfactant oil displacements composition and Shuan He oil fields5-11 series of strata oil water interfacial tension results
| Embodiment | Interfacial tension (mN/m) |
| 1 b | 0.0095 |
| 2 b | 0.0088 |
| 3 b | 0.0055 |
| 4 b | 0.0093 |
| 5 b | 0.0002 |
| 6 b | 0.0075 |
| 7 b | 0.0021 |
| 8 b | 0.0064 |
| 9 b | 0.0005 |
| 10 b | 0.0006 |
| 11 b | 0.0040 |
From the b of table 2, compound surfactant prepared by the b of the b of embodiment 1~10 has good for Henan Oil Field
Interface performance.The b of embodiment 11 shows that after surfactant prepared by the present invention is compounded with polymer, its interface performance is still
Well.
The b of embodiment 10 surface activator compositions prepared are configured to various concentrations, respectively test and Shuanghe in Henan's oil
Field5-11 series of strata oil water interfacial tensions, the results are shown in Table 3 b.
The b of table 3b various concentrations surface activator composition 10 and Shuanghe Oil Field5-11 series of strata oil water interfacial tensions
| Dosage of surfactant (%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.009 | 0.007 | 0.005 | 0.002 | 0.0009 | 0.0006 |
The above results show that surfactant oil displacement composition of the present invention has very high boundary for Henan Oil Field crude oil
Face activity.
The surface activator composition of the b of embodiment 5 preparations is determined again with TX-500C rotating interfacial tensimeters with
The former factory's oil water interfacial tension of oil extraction in oil field three.It is 80 to determine temperatureoC, formation water salinity is 79439mg/L, Ca2+Content 592
Mg/L, Mg2+Content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.004mN/m, shows this
The surfactant of invention still has well interface characteristics not only for low mineralization oil reservoir simultaneously for high temperature and high salt oil deposit
Can, have the advantages that the scope of application is wide.
【The b of embodiment 13】Surface activator composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sands, according to oil：Sand=1：4 (weight ratios) are 81oC agings 7 days, every 2 is small
When stir 5 minutes；The oil-sand 5g after above-mentioned aging is then taken out, oil-sand is pressed with 0.3 wt % surfactant solution：Solution=
1：10（Weight ratio）It is well mixed, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, use 50ml
Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Utilize standard curve gauging surface activator solution Central Plains
Oil concentration.
Table 4b surfactant washing oil results
| Embodiment | Washing oil rate % |
| 1 b | 65.3 |
| 2 b | 63.9 |
| 3 b | 47.6 |
| 4 b | 60.3 |
| 5 b | 46.2 |
| 6 b | 54.4 |
| 7 b | 48.5 |
| 8 b | 61.3 |
| 9 b | 55.1 |
| 10 b | 52.2 |
【The b of embodiment 14】Surface activator composition Oil Displacing Capacity is studied
It it is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns2Rock core on carry out oil displacement test.First
Use Shuanghe Oil Field5-11 series of strata stratum water drive to aqueous 92 wt %, metaideophone 0.3pv (rock pore volume) surface is lived
Property agent composition after, water drive to aqueous 100 wt %, improve oil recovery factor the results are shown in Table 5.
Table 5b surface activator composition oil displacement test results
| Embodiment | Improve recovery ratio % |
| 1 b | 7.2 |
| 2 b | 6.0 |
| 3 b | 5.6 |
| 4 b | 5.3 |
| 5 b | 6.6 |
| 6 b | 5.8 |
| 7 b | 5.5 |
| 8 b | 6.2 |
| 9 b | 6.5 |
| 10 b | 6.3 |
Claims (8)
1. a kind of surfactant oil displacement composition, including cationic surfactant and Anionic-nonionic surface-active
Agent, described cationic surfactant and the mol ratio of Anionic-nonionic surfactant are 1: 0.01~1: 100, its
Cationic surfactant is selected from least one of quaternary ammonium salt or quaternary amine alkali, Anionic-nonionic surfactant molecule
Formula is：
Wherein M is any one in alkali metal, alkaline-earth metal, ammonium root；R is H, C1~C20Alkyl, C6~C10Aryl or
Any one in substituted aryl；R ' is C1~C10Alkylidene；M, n are any one integer in 1~10；X be more than 0 and
Any one integer or decimal in less than 100；Y is any one integer or decimal in 0~100；R is M in general molecular formula
With SO3The mol ratio of group or M and COO groups, the r=1 when M is alkali metal or ammonium root, the r=when M is alkaline-earth metal
0.5。
2. surfactant oil displacement composition according to claim 1, it is characterised in that x is appointing more than 0 and less than 50
One integer of meaning or decimal, y are any one integer or decimal in 0~50.
3. surfactant oil displacement composition according to claim 1, it is characterised in that the cationic surfactant
Selected from least one of tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
4. surfactant oil displacement composition according to claim 1, it is characterised in that the cationic surfactant
Carbon number in molecule is 4~40.
5. surfactant oil displacement composition according to claim 1, it is characterised in that R ' is C1~C5Alkylidene.
6. the preparation method of surfactant oil displacement composition, is comprised the steps of described in claim 1：
A) unrighted acid, acidic catalyst and aromatic hydrocarbon are added into reactor, it is small in 50~150 DEG C of addition reactions 1~20
When, wherein unrighted acid：Aromatic hydrocarbons mol ratio is 1：(0.5~1.0)；After reaction terminates, in 100~300 DEG C of temperature, pressure
10~100kg/cm2Hydrogenation reaction 1~10 hour, so that aryl substituted carboxylic acid is reduced into aryl substituted alcohols；Aryl is replaced
Alcohol, base catalyst and required expoxy propane, oxirane add reactor, in 100~200 DEG C carry out etherification reactions 1~
20 hours；Then add sulfonated reagent or carboxylating reagent carry out sulfonation/carboxylation reaction, reacted 1~20 hour in 50~100 DEG C,
Wherein aryl replaces fatty alcohol polyoxypropylene APEO：The mol ratio of sulfonated reagent/carboxylating reagent is 1：(1~4)；Reaction
After end, adjusted with acidic aqueous solution to pH=1~3, carry out water-oil separating, oil phase adds alkali lye and is neutralized to pH=7~9, obtains
Replace fatty alcohol polyoxypropylene polyethenoxy ether sulphonate or aryl substitution fatty alcohol polyoxypropylene APEO carboxylic to aryl
Hydrochlorate Anionic-nonionic surfactant；
B) the Anionic-nonionic surfactant obtained by cationic surfactant and according to step a) is dissolved separately in
It is then well mixed according to mol ratio 1: 0.1~1: 10 in water.
7. the preparation method of surfactant oil displacement composition according to claim 6, it is characterised in that step a) is described
Base catalyst is selected from least one of NaOH or KOH.
8. application of the surfactant oil displacement composition in the displacement of reservoir oil of oil field any one of claim 1 to 5.
Priority Applications (1)
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| CN106867494B (en) * | 2015-12-14 | 2020-10-16 | 中国石油化工股份有限公司 | Combined surfactant with strong crude oil solubilizing capability and low-cost preparation method |
| CN106867495B (en) * | 2015-12-14 | 2020-10-16 | 中国石油化工股份有限公司 | Composite surfactant and low-cost preparation method thereof |
| CN108479631B (en) * | 2018-03-19 | 2021-06-04 | 青岛大学 | Anionic nonionic surfactant and preparation method thereof |
| CN111088005B (en) * | 2018-10-23 | 2022-10-11 | 中国石油化工股份有限公司 | Method for enhancing injection performance of surfactant composition for oil displacement, composition, preparation method and application thereof |
| CN112708410B (en) * | 2019-10-25 | 2023-01-24 | 中国石油化工股份有限公司 | Composite surfactant containing aryl alcohol polyether anionic nonionic surfactant |
| CN112795002B (en) * | 2019-11-14 | 2022-04-01 | 中国石油化工股份有限公司 | Polyether anionic and nonionic surfactant containing heteroatom and preparation method thereof |
| CN113930229B (en) * | 2020-07-14 | 2023-05-02 | 中国石油化工股份有限公司 | Oil displacement agent containing quaternary ammonium salt surfactant composition, and preparation method and application thereof |
| CN118064929B (en) * | 2024-04-19 | 2024-07-02 | 保时来新材料科技(苏州)有限公司 | Raney nickel catalyst activation additive and preparation method and application thereof |
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