CN104232045B - Composite surface active agent composition and preparation method and application thereof - Google Patents
Composite surface active agent composition and preparation method and application thereof Download PDFInfo
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- CN104232045B CN104232045B CN201310237545.XA CN201310237545A CN104232045B CN 104232045 B CN104232045 B CN 104232045B CN 201310237545 A CN201310237545 A CN 201310237545A CN 104232045 B CN104232045 B CN 104232045B
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 171
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title abstract 3
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 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
- 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 97
- -1 alkyl phenol Chemical compound 0.000 claims description 80
- 150000001875 compounds Chemical class 0.000 claims description 79
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 239000002736 nonionic surfactant Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 48
- 239000003153 chemical reaction reagent Substances 0.000 claims description 38
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 38
- 239000012190 activator Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000003093 cationic surfactant Substances 0.000 claims description 20
- 150000001768 cations Chemical class 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000005466 alkylenyl group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005815 base catalysis Methods 0.000 claims 1
- 150000003977 halocarboxylic acids Chemical group 0.000 claims 1
- 210000000952 spleen Anatomy 0.000 claims 1
- 210000002784 stomach Anatomy 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 abstract description 20
- 125000002091 cationic group Chemical group 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 177
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 40
- 238000003756 stirring Methods 0.000 description 39
- 239000012071 phase Substances 0.000 description 38
- 150000002191 fatty alcohols Chemical class 0.000 description 35
- 241001272567 Hominoidea Species 0.000 description 33
- 238000013517 stratification Methods 0.000 description 26
- 239000008346 aqueous phase Substances 0.000 description 24
- 229920001451 polypropylene glycol Polymers 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000010779 crude oil Substances 0.000 description 21
- 229910052791 calcium Inorganic materials 0.000 description 19
- 239000011575 calcium Substances 0.000 description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 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 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000007900 aqueous suspension Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 10
- 239000011435 rock Substances 0.000 description 10
- 239000003945 anionic surfactant Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 239000003027 oil sand Substances 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 239000003129 oil well Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 5
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 208000014674 injury Diseases 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- GQFZYTXZJHSSEA-UHFFFAOYSA-M decyl(triethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CC)(CC)CC GQFZYTXZJHSSEA-UHFFFAOYSA-M 0.000 description 3
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000008398 formation water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229940057874 phenyl trimethicone Drugs 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 229940045998 sodium isethionate Drugs 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 3
- 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 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 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
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007787 solid Substances 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
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-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
- 239000004593 Epoxy Substances 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 229910003202 NH4 Inorganic materials 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
- 238000010795 Steam Flooding Methods 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 238000013329 compounding 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
- 238000005304 joining Methods 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
- 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
- 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
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 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
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention relates to a composite surface active agent composition, and a preparation method and application thereof, and mainly solves the problems of poor displacement efficiency in a tertiary oil recovery process, and harm to the stratum and the oil field, corrosion of equipment and pipeline and difficult demulsification due to oil inorganic alkali contained in displacement system. The invention adopts the composite surface active agent composition comprising a cationic surface active agent and an anionic-non-ionic surface active agent in the molar ratio of 1:0.01 to 1:100. The cationic surface active agent is at least one selected from the group consisting of quaternary ammonium salt or quaternary ammonium alkali; and the anionic-non-ionic surface active agent is represented by a molecular general formula shown as below, wherein M represents one of an alkali metal, an alkaline earth metal and ammonium. The technical scheme well solves the above problems, and can be used in tertiary oil recovery process.
Description
Technical field
The present invention relates to compound surfactant composition, preparation method and its application in tertiary oil recovery.
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.Realize the high-efficiency mining of petroleum resources, for raising crude output not
Only there is realistic meaning, with more important strategic importance.Conventional oil production method（Once with 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 that energy day is becoming tight, improves tar productivity
The key subjects of oil exploitation research are become.Tertiary oil recovery technology is then a kind of effective method improving tar productivity, can divide
For four big class：One is that heating power drives, including steam drive, combustion in situ etc.；Two is that mixed phase drives, including CO2Mixed phase, hydrocarbon mixed phase and other
Inert gas mixed phase drives；Three is chemical flooding；Four is microbe oil production, drives including biopolymer, MICROBIAL SURFACTANT.Change
Learning drive is 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 combination technology of polymer, alkali, surfactant.The effect of chemical flooding is the knot of physical action and 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（Hydrophobic）With 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 little oil
Drip, thus improving crude oil to flow through percent of pass during pore throat.The oil displacement efficiency of surfactant is also manifested by making 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 play very important effect in technology.
Surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly at present, comprises non-ionic surfactant simultaneously
Agent and ionic surfactant, are additionally added the auxiliary agents such as alkali and alcohol in part formulation.As patent CN101024764A provides one
The surfactant of kind of oil-field thick-oil well, this activating agent be by water, piece alkali, ethanol, oleic acid, APES, ten
Dialkyl benzene sulfonic acids sodium forms.For another example patent CN1458219A discloses a kind of surfactant polymer of tertiary oil recovery application
Pure binary ultralow interfacial tension combination flooding formula, used in it, surfactant is petroleum sulfonate or with petroleum sulfonate is
Host adds diluent and the complexed surfactant of other surfactant compound, 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
As patent CN1394935 has invented a kind of chemical oil displacement agent, 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, can reduce oil water interfacial tension simultaneously, thus improving 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 breakdown of emulsion is difficult, and sewage disposal difficulty is big；Separately
Outward because oil displacement system contains inorganic base, injury is brought to stratum and oil well, causes the problems such as 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 reaching required viscosity, make
Oil recovery integrated cost improves；The high temperature resistance of surfactant, high salt tolerance, anti-high salinity limited in one's ability.
It is known that anion surfactant, such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate etc. are at present
During being widely used in tertiary oil recovery, and cationic surfactant is easily adsorbed or produced by stratum precipitation because of it, therefore fall
The ability of low oil water interfacial tension, is generally not used for tertiary oil recovery.Because cationic and anionic surfactant mixes close to equal proportion
During conjunction, its aqueous solution easily forms precipitation, thus lead to cationic and anionic surfactant mixed system not only to become in the application joining
5 taboos, and correlation theory research is also more delayed.Research in recent years finds, cationic and anionic surfactant mixed system
The aqueous solution has a lot of anomalous properties, such as because cationic and anionic surfactant has strong electrostatic interaction in aqueous
Interaction and between hydrophobic carbon chain, promotes two kinds of band difference interionic associations of charged surfactant, in the solution
It is readily formed micella, the higher surface-active of the single surfactant of producing ratio.Additionally, cationic and anionic surfactant mixing
System can obviously reduce absorption loss on rock core for the cationic surfactant, thus cation surface activating can be significantly reduced
The inherent shortcoming of agent.
Gong Yujun etc.（See 2 months the 1st phases Northwest University's journal (natural science edition) of volume 30 in 2000,28～31）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 ", under the oil wash that will stick on the sandstone of rock stratum, thus improve oil adopting
Yield.Huang Hongdu etc.（See petroleum gas journal in August, 2007 the 4th phase of volume 29,101～104）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
Still employ alkali, thus alkali cannot be avoided to bring injury, etching apparatus and pipeline and breakdown of emulsion difficulty etc. to ask on stratum and oil well
Topic.In addition above-mentioned system is easier to generate precipitation, is unfavorable for practical application.
For this reason, one aspect of the present invention absorbs has used for reference forefathers with regard to anions and canons Surfactants mixed system research knot
Really, on the other hand adopt Anionic-nonionic surfactant to replace traditional anion surfactant, overcome yin, yang
The shortcomings of ionic surface active agent easily precipitates when compounding, has invented the cation surface activating for improving oil recovery factor
Agent and Anionic-nonionic surfactant compound surfactant composition.
Content of the invention
One of the technical problem to be solved is existing surfactant oil displacement efficiency during tertiary oil recovery
Difference, simultaneously because oil displacement system contains inorganic base, brings injury, etching apparatus and pipeline and breakdown of emulsion difficult to stratum and oil well
Problem, provides a kind of new compound surfactant 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, will not etching apparatus and pipeline and the advantage not resulting in breakdown of emulsion difficulty.
The two of the technical problem to be solved are to provide a kind of surface corresponding with solving technical problem one to live
The preparation method of property agent composition.
The three of problem to be solved by this invention are the described surface activator compositions of one of above-mentioned technical problem at three times
Application in oil recovery.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：Compound surfactant combines
Thing, including cationic surfactant and Anionic-nonionic surfactant, described cationic surfactant with 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 in amine base, Anionic-nonionic surfactant is by following general molecular formula（A）、（B）、（C）Or（D）Represent：
（A）、(B)、
（C）、（D）；
Wherein M is any one in alkali metal, alkaline-earth metal or ammonium root, and R is H, C1~C20Alkyl, C6~C10Aryl
Or any one in substituted aryl, m and n independence value is any one integer or decimal in 0～100；R is C1～C10
Alkylidene；R is M and SO in general molecular formula3Group or the mol ratio of M and COO group, the r=when M is for alkali metal or ammonium root
1, when M is for alkaline-earth metal, r=0.5；R1For C1~C50Alkyl or alkenyl.
Preferable m in technique scheme>0；For general molecular formula（C）With（D）Live in shown Anionic-nonionic surface
Property agent optional m further>0 and n>0.
Cationic surfactant described in technique scheme preferably is selected from tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide
In at least one.Carbon number in described cationic surfactant molecule is preferably 4 ~ 40.Described Anionic-nonionic
Surfactant cationic M preferably is selected from Na, K, Mg, Ca or NH4In any one.R is preferably H, C5～C15Alkyl or
Aryl.R1It is preferably C5～C20Alkyl, thiazolinyl.R is preferably C1～C5Alkylidene.
In technique scheme, m and n is preferably any one integer in 0～50 or decimal.
Cationic surfactant described in technique scheme is excellent with the mol ratio of Anionic-nonionic surfactant
Scope is selected to be 1: 0.1～1: 10.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：One of above-mentioned technical problem is described
Described in technical scheme, the preparation method of compound surfactant composition, comprises the following steps：
A) by alkyl phenol polyoxyethylene polyoxypropylene ether, catalyst according to mol ratio 1:(1～5) add reactor, in room
Temperature～100oC alkalizes 1～10 hour, then adds sulfonated reagent or carboxylating reagent, wherein alkyl phenol polyoxyethylene polyoxypropylene
Ether：The mol ratio of sulfonated reagent or carboxylating reagent is 1：(1～4), is warming up to 50～100oC reacts 1～20 hour, post-treated
Obtain alkyl phenol polyoxyethylene polyoxypropylene ether sulfonate or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylate；Described post processing
Preferably include to use acidic aqueous solution（For example aqueous hydrochloric acid solution, aqueous sulfuric acid, phosphate aqueous solution, sodium bisulphate solution or
Aqueous potassium hydrogen sulfate）Adjust to pH=1 ~ 3, carry out water-oil separating, oil phase adds alkali lye to be neutralized to pH=7 ~ 9；Described
The preferred base catalyst of catalyst, described catalyst is more preferably alkali metal hydroxide, in most preferably NaOH or KOH at least
A kind of；Described sulfonated reagent is preferably hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Described carboxylating reagent is preferably
Halogenated carboxylic acid and its salt；
B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is molten respectively
In Xie Yushui, then mix according to mol ratio (1: 0.1)～(1: 10), obtain described surface activator composition.
For solving the three of above-mentioned technical problem, technical scheme is as follows：Any one of one of technical problem technology
Application in tertiary oil recovery for the compound surfactant composition described in scheme.
The compound surfactant composition one side of the present invention is due to anions and canons surfactant opposite charges pole
Property base between strong electrostatic attraction effect so that surfactant molecule adsorbed on interfaces amount increase, critical micelle concentration
Significantly reduce, thus having the incomparable high surface of single surfactant；Simultaneously because compound surfactant
The interfacial activity of superelevation, its aqueous solution can form ultralow interfacial tension with crude oil, thus effectively overcoming the cohesive force between crude oil, has
Beneficial to the outflow of crude oil, and then oil displacement efficiency is greatly improved.Another aspect compound surfactant composition can change oil
Cationic surfactant in the wetability of layer surface, such as composition is by the electronegative base on a solid surface with absorption
Group interacts so as to be desorbed, and makes glossy wet structure change into neutral wetting or water-wet surface, reduces crude oil in solid
The adhesion work on surface, thus be conducive to the stripping of crude oil.Anions and canons surfactant mixed solution has increasing to crude oil simultaneously
Molten effect, can wash down sticking to the crude oil on the sandstone of rock stratum further, improve oil recovery factor.
Adopt compound surfactant composition of the present invention during tertiary oil recovery, there is interfacial activity high：Compound
Surface activator composition consumption be 0.01～0.05wt% under the conditions of remain to and underground crude oil formed 10-3～10-4MN/m
Ultralow interfacial tension；Washing oil ability is strong：Compound surfactant composition is to the washing oil rate of crude oil more than 40%；Surface-active
Agent composition system is simple.Because system does not contain inorganic base, thus the wound that when avoiding scene application, inorganic base causes to stratum
Evil, the corrosion that equipment is caused and the problem of the breakdown of emulsion difficulty thus causing, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：5 addition reactors, in 100oC alkalization 1 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, are cooled to
50oC continues reaction 20 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 1, and stratification divides and goes
Aqueous phase, oil phase is neutralized to pH value 7 with the 10 wt %NaOH aqueous solution, and vacuum removal moisture obtains alkyl phenol polyoxypropylene polyoxy second
Alkene ether sulfonic acid sodium.
Alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid sodium table by hexadecyltrimethylammonium chloride and present invention preparation
Face activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to
Cation：Anionic-nonionic surfactant molar ratio 1: 0.3 mixes, and obtains compound surfactant composition
1a, its composition, structure are shown in Table 1a.
【Embodiment 2a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1 addition reactor is little in room temperature alkalization 10
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, are warming up to
70oC continues 10 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2.5, and stratification divides and removes water
Phase, oil phase is neutralized to pH value 9 with 10 wt % ammoniacal liquor, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid
Ammonium.
Lived in the alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium surface of benzyltriethylammoinium chloride and present invention preparation
Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun
Ion：Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, and obtains compound surfactant composition 2
A, its composition, structure are shown in Table 1 a.
【Embodiment 3a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1.5 addition reactors, in 30oC alkalization 8 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chlorine amyl group sodium sulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to
60oC continues 15 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes water
Phase, oil phase is with 10 wt %Ca (OH)2Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxypropylene polyoxy
Vinethene sulfoacid calcium.
Alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid calcium table by phenyl trimethicone ammonium chloride and according to present invention preparation
Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, and obtains compound surfactant 3 a,
Its composition, structure are shown in Table 1 a.
【Embodiment 4a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：2 addition reactors, in 50oC alkalization 6 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：2 addition sulfonated reagents,
It is warming up to 80oC continues 8 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, stratification, point
Remove aqueous phase, oil phase is with 10 wt %Mg (OH)2Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxypropylene
APEO sulfonic acid magnesium.
Alkyl phenol polyoxyethylene polyoxypropylene ether by stearyl dimethyl benzyl ammonium chloride and according to present invention preparation
Sulfonic acid magnesium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface
Activating agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 2.0 mixes, and obtains compound surface and lives
Property agent 4 a, its composition, structure be shown in Table 1 a.
【Embodiment 5a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：3 addition reactors, in 60oC alkalization 5 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Monoxone mol ratio 1：1 addition carboxylating reagent, is warming up to 100oC continues
Continuous 1 hour.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is used
The 10 wt %NaOH aqueous solution are neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium.
Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium by decyl triethylammonium hydroxide and according to present invention preparation
Surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 10 mixes, and obtains compound surfactant 5 a,
Its composition, structure are shown in Table 1 a.
【Embodiment 6a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：4 addition reactors, in 80oC alkalization 2 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloropropionic acid mol ratio 1：1.5 addition carboxylating reagent, are cooled to 50oC
Continue 18 hours, then add hydrochloric acid to be neutralized to pH<3, and carry out water-oil separating, oil phase adds 10%Ca (HCO3)2It is neutralized.
After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %
Ca(OH)2Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether calcium carboxylates.
Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid by DTAC and according to present invention preparation
Calcium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface-active
Agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 0.9 mixes, and obtains compound surfactant 6
A, its composition, structure are shown in Table 1 a.
【Embodiment 7a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1 addition reactor is little in room temperature alkalization 10
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Sodium chloroacetate mol ratio 1：3 addition carboxylating reagent, are warming up to 80oC
Continue 8 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase
It is neutralized to pH value 8 with the 10 wt %KOH aqueous solution, vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid potassium.
Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic by dioctadecyl dimethyl ammonium chloride and according to present invention preparation
Sour potassium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then lives in above-mentioned surface
Property agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains compound surfactant 7
A, its composition, structure are shown in Table 1 a.
【Embodiment 8a】
By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：3 addition reactors, in 65oC alkalization 2 is little
When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloropropionic acid mol ratio 1：2 addition carboxylating reagent, are warming up to 75oC continues
Continuous 9 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is used
The 10 wt %NaOH aqueous solution are neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium.
Live by four octyl group ammonium chlorides and according to the alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium surface of present invention preparation
Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun
Ion：Anionic-nonionic surfactant molar ratio 1: 6 mixes, and obtains compound surfactant 8 a, its composition,
Structure is shown in Table 1 a.
【Embodiment 9a】
By the 0.30wt% compound surfactant of embodiment 3 a preparation and 0.15wt% polyacrylamide (molecular weight
26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1a compound surfactant composition composition and structure
【Embodiment 10 a】Compound surfactant composition interface performance is tested
Measure compound surfactant composition and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5-
11 series of strata oil water interfacial tensions.Temperature of the measurement is 81oC, stratum water is NaHCO3Type, salinity is 7947mg/L, chloride ion content
2002 mg/L, Ca2+Content 20 mg/L, Mg2+Content 12.2 mg/L, compound surfactant composition consumption is 0.3 wt
%.
Table 2a compound surfactant composition and Shuan He oil field5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 a | 0.0071 |
| 2 a | 0.0087 |
| 3 a | 0.0002 |
| 4 a | 0.0004 |
| 5 a | 0.0059 |
| 6 a | 0.0068 |
| 7 a | 0.0007 |
| 8 a | 0.0062 |
| 9 a | 0.0051 |
From table 2a, the compound surfactant of embodiment 1a～8a preparation has good boundary for Henan Oil Field
Face performance.Embodiment 9a shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still good.
The compound surfactant of embodiment 3a preparation is configured to variable concentrations, respectively test and Shuanghe Oil Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3a.
Table 3a variable concentrations surface activator composition 3a and Shuanghe Oil Field5-11 series of strata oil water interfacial tension
| Dosage of surfactant (wt%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.006 | 0.003 | 0.001 | 0.0006 | 0.0004 | 0.0002 |
The above results show, compound surfactant composition of the present invention has very high oil for Henan Oil Field crude oil
Water termination activity.
With TX-500C rotating interfacial tensimeter measure again embodiment 4 a preparation compound surfactant with
Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80oC, 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 0.003mN/m, shows this
The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit
Can, have the advantages that the scope of application is wide.
【Embodiment 11a】Compound surfactant composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81oAging 7 days of C, every 2 is little
When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil-sand with the surfactant solution of 0.3 wt %：Solution
Weight ratio=1：10 mix, and after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, use 50ml
Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activator solution Central Plains
Oil concentration.
Table 4a compound surfactant composition washing oil result
| Embodiment | Washing oil rate % |
| 1 a | 63.8 |
| 2 a | 61.4 |
| 3 a | 45.8 |
| 4 a | 59.2 |
| 5 a | 41.5 |
| 6 a | 53.5 |
| 7 a | 58.9 |
| 8 a | 46.7 |
【Embodiment 12 a】Compound surfactant composition Oil Displacing Capacity is studied
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 produces to oil-free, the compound table of metaideophone 0.3PV (rock pore volume)
After the surfactant composition of face, then water drive produces to oil-free, improves oil recovery factor and the results are shown in Table 5 a.
Table 5a compound surfactant composition oil displacement test result
| Surfactant sequence number | Improve recovery ratio % |
| 1 a | 6.3 |
| 2 a | 5.9 |
| 3 a | 6.1 |
| 4 a | 6.7 |
| 5 a | 5.2 |
| 6 a | 5.5 |
| 7 a | 6.9 |
| 8 a | 5.3 |
【Comparative example 1a】
According to Northwest University's journal (natural science edition) 2 months the 1st phases of volume 30 in 2000, 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),
Test it respectively in 0.3 wt % consumption and Shuanghe Oil Field5-11 series of strata crude oil oil water interfacial tension, washing oil rate and drive
Oiliness energy, result is as follows：
Table 6a reference oil displacement agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.03 | 45.6 | 2.8 |
【Comparative example 2a】
According to petroleum gas journal in August, 2007 the 4th phase of volume 29, Huang Hong degree etc. (101～104) method etc. is by 0.01
Wt % cetyl trimethylammonium bromide and 0.02 wt % anion surfactant petroleum sulfonate and 1.8 wt %Na2CO3
It is configured to mixed system, test it respectively in 0.3 wt % consumption and Shuanghe Oil Field5-11 series of strata crude oil oil-water interfaces
Tension force, washing oil rate and Oil Displacing Capacity, result is as follows：
Table 7a reference oil displacement agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.008 | 56.3 | 4.2 |
【Embodiment 1b】
By APES, NaOH according to mol ratio 1：5 addition reactors, in 100oC alkalizes 1 hour, then
According to APES：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, are cooled to 50oIt is little that C continues reaction 20
When, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is water-soluble with 10 wt %NaOH
Liquid is neutralized to pH value 8, and vacuum removal moisture obtains APES sodium sulfonate.
APES sulfonate surfactants by hexadecyltrimethylammonium chloride and present invention preparation
It is dissolved in water, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation：
Anionic-nonionic surfactant molar ratio 1: 0.3 mixes, and obtains compound surfactant composition 1 b, its group
Become, structure is shown in Table 1 b.
【Embodiment 2b】
By APES, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses
According to APES：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, are warming up to 70oC continuation 10 hours, so
Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution afterwards is 2, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value with 10 wt % ammoniacal liquor
8, vacuum removal moisture obtains APES ichthyodin.
By the APES sulfonic acid ammonium surfactant of benzyltriethylammoinium chloride and present invention preparation respectively
It is dissolved in the water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to cation：Cloudy
Ion-nonionic surfactant mol ratio 1: 0.1 mixes, and obtains compound surfactant composition 2 b, its group
Become, structure is shown in Table 1 b.
【Embodiment 3b】
By APES, KOH according to mol ratio 1：1.5 addition reactors, in 30oC alkalizes 8 hours, then
According to APES：Chlorine amyl group sodium sulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 60oC continues 15 hours,
Then being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)2Water
Suspension is neutralized to pH value 8, and vacuum removal moisture obtains APES sulfoacid calcium.
APES sulfoacid calcium surfactant by phenyl trimethicone ammonium chloride and according to present invention preparation
Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, and obtains compound surfactant 3 b, its composition,
Structure is shown in Table 1 b.
【Embodiment 4b】
By APES, NaOH according to mol ratio 1：2 addition reactors, in 50oC alkalizes 6 hours, then presses
According to APES：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 80oIt is little that C continues 8
When, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)2's
Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains APES sulfonic acid magnesium.
APES sulfonic acid magnesium table by stearyl dimethyl benzyl ammonium chloride and according to present invention preparation
Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 2.0 mixes, and obtains compound surfactant 4 b,
Its composition, structure are shown in Table 1 b.
【Embodiment 5b】
By APES, NaOH according to mol ratio 1：3 addition reactors, in 60oC alkalizes 5 hours, then presses
According to APES：Monoxone mol ratio 1：1 addition carboxylating reagent, is warming up to 100oC continues 1 hour, Ran Houyong
It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, and oil phase is neutralized with the aqueous suspension of 10 wt %NaOH
To pH value 8, vacuum removal moisture obtains APES carboxylic acid sodium.
APES carboxylic acid sodium surface-active by decyl triethylammonium hydroxide and according to present invention preparation
Agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 10 mixes, and obtains compound surfactant 5 b, its composition,
Structure is shown in Table 1 b.
【Embodiment 6b】
By APES, NaOH according to mol ratio 1：4 addition reactors, in 80oC alkalizes 2 hours, then presses
According to APES：Chloropropionic acid mol ratio 1：1.5 addition carboxylating reagent, are cooled to 50oC continues 18 hours, Ran Houyong
It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)2Aqueous suspension
It is neutralized to pH value 8, vacuum removal moisture obtains APES calcium carboxylates.
Live by DTAC and according to the APES calcium carboxylates surface of present invention preparation
Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun
Ion：Anionic-nonionic surfactant molar ratio 1: 0.9 mixes, and obtains compound surfactant 6 b, its group
Become, structure is shown in Table 1 b.
【Embodiment 7b】
By APES, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses
According to APES：Sodium chloroacetate mol ratio 1：3 addition carboxylating reagent, are warming up to 80oC continues 8 hours, Ran Houyong
It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH with the 10 wt %KOH aqueous solution
Value 8, vacuum removal moisture obtains APES carboxylic acid potassium.
APES carboxylic acid potassium surface by dioctadecyl dimethyl ammonium chloride and according to present invention preparation
Activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to
Cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains compound surfactant 7 b, its group
Become, structure is shown in Table 1 b.
【Embodiment 8b】
By APES, NaOH according to mol ratio 1：3 addition reactors, in 65oC alkalizes 2 hours, then presses
According to APES：Chloropropionic acid mol ratio 1：2 addition carboxylating reagent, are warming up to 75oC continues 9 hours, then uses 5wt%
It is 2 that aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution,
Vacuum removal moisture obtains APES carboxylic acid sodium.
APES carboxyl acid natrium surfactant difference by four octyl group ammonium chlorides and according to present invention preparation
It is dissolved in the water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to cation：Cloudy
Ion-nonionic surfactant mol ratio 1: 6 mixes, and obtains compound surfactant 8 b, and its composition, structure are shown in
Table 1 b.
【Embodiment 9b】
By the 0.30wt% compound surfactant of embodiment 3 b preparation and 0.15wt% polyacrylamide (molecular weight
26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1b compound surfactant composition composition and structure
【Embodiment 10 b】Compound surfactant composition interface performance is tested
Measure compound surfactant composition and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5-
11 series of strata oil water interfacial tensions.Temperature of the measurement is 81oC, stratum water is NaHCO3Type, salinity is 7947mg/L, chloride ion content
2002 mg/L, Ca2+Content 20 mg/L, Mg2+Content 12.2 mg/L, compound surfactant composition consumption is 0.3 wt
%.
Table 2b compound surfactant composition and Shuan He oil field5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 b | 0.0080 |
| 2 b | 0.0096 |
| 3 b | 0.0004 |
| 4 b | 0.0006 |
| 5 b | 0.0068 |
| 6 b | 0.0075 |
| 7 b | 0.0011 |
| 8 b | 0.0075 |
| 9 b | 0.0062 |
From table 2 b, the compound surfactant of embodiment 1 b～8 b preparation has well for Henan Oil Field
Interface performance.Embodiment 9 b shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still
Well.
The compound surfactant of embodiment 3 b preparation is configured to variable concentrations, respectively test and Shuanghe in Henan's oil
Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3 b.
Table 3b variable concentrations surface activator composition 3 b and Shuanghe Oil Field5-11 series of strata oil water interfacial tension
| Dosage of surfactant (%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.009 | 0.007 | 0.004 | 0.002 | 0.0007 | 0.0004 |
The above results show, compound surfactant composition of the present invention has very high oil for Henan Oil Field crude oil
Water termination activity.
With TX-500C rotating interfacial tensimeter measure again embodiment 4 b preparation compound surfactant with
Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80oC, 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 0.003mN/m, shows this
The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit
Can, have the advantages that the scope of application is wide.
【Embodiment 11 b】Compound surfactant composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81oAging 7 days of C, every 2 is little
When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil-sand with the surfactant solution of 0.3 wt %：Solution=
1：10 (weight ratios) mix, and after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, use 50ml
Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activator solution Central Plains
Oil concentration.
Table 4b compound surfactant composition washing oil result
| Embodiment | Washing oil rate % |
| 1 b | 62.5 |
| 2 b | 60.1 |
| 3 b | 44.3 |
| 4 b | 58.1 |
| 5 b | 40.8 |
| 6 b | 52.4 |
| 7 b | 57.6 |
| 8 b | 45.5 |
【Embodiment 12b】Compound surfactant composition Oil Displacing Capacity is studied
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 Field, to aqueous 92 wt %, metaideophone 0.3pv's (rock pore volume) is compound for 5-11 series of strata stratum water drive
After surface activator composition, water drive to aqueous 100%, improves oil recovery factor and the results are shown in Table 5 b.
Table 5b compound surfactant composition oil displacement test result
| Surfactant sequence number | Improve recovery ratio % |
| 1 b | 5.5 |
| 2 b | 5.1 |
| 3 b | 5.2 |
| 4 b | 5.9 |
| 5 b | 4.4 |
| 6 b | 4.7 |
| 7 b | 6.1 |
| 8 b | 4.5 |
【Embodiment 1c】
By C5H11OH, NaOH are according to mol ratio 1：5 and, stir 30 minutes, then add required expoxy propane, in
140oC reacts 10 hours, then adds required oxirane, in 140oC reaction is reacted 1 hour again；Then according to C5H11OH
With sodium chloroacetate mol ratio 1：1 addition carboxylating reagent, in 50oC continues reaction 20 hours, then uses 5wt% aqueous hydrochloric acid solution to neutralize
It is 2 to pH value, stratification, divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution, and vacuum removal moisture obtains
To Anionic-nonionic surfactant.
The Anionic-nonionic surfactant of phenyl trimethicone ammonium chloride and present invention preparation is dissolved separately in water
In, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic
Surfactant molar ratio 1: 10 mixes, and obtains surface activator composition 1 c, and its composition, structure are shown in Table 1 c.
【Embodiment 2c】
By fatty alcohol C20H41OH, KOH are according to mol ratio 1：2.5, stirring adds required expoxy propane after 30 minutes, in
100oC reacts 10 hours；Then add the desired amount of oxirane, in 140oC reacts 10 hours, then according to fatty alcohol polyoxy
Propylene APEO：ClCH2CH2COOH mol ratio 1：1.5 addition carboxylating reagent, in 100oC continues reaction 1 hour, Ran Houyong
It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH with the 10 wt %KOH aqueous solution
Value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic acid potassium.
Fatty alcohol polyoxypropylene APEO carboxylic acid potassium surface by decyl triethylammonium hydroxide and present invention preparation
Activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to
Cation：Anionic-nonionic surfactant molar ratio 1: 7 mixes, and obtains surface activator composition 2 c, its group
Become, structure is shown in Table 1 c.
【Embodiment 3c】
By fatty alcohol C14H29OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 5 hours；Then add required oxirane, in 160oC reacts 6 hours；Then according to fatty alcohol polyoxypropylene
APEO：ClCH2COOH mol ratio 1：1.5 addition carboxylating reagent, in 70oC continues reaction 8 hours, then uses 5wt% hydrochloric acid
It is 2 that the aqueous solution is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)2Aqueous suspension is neutralized to pH value
8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic acid potassium.
Fatty alcohol polyoxypropylene APEO carboxylic acid potassium surfactant by etamon chloride and present invention preparation
Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 1.3 mixes, and obtains surface activator composition 3 c, its composition,
Structure is shown in Table 1 c.
【Embodiment 4c】
By fatty alcohol C16H33OH, NaOH are according to mol ratio 1：5 and, stir 30 minutes, then add required epoxy third
Alkane, in 140oC reacts 1 hour, then adds required oxirane, in 140oC reaction is reacted 4 hours again；Then according to fat
Fat alcohol polyoxyethylene polyoxypropylene ether：ClCH2COOH mol ratio 1：2 addition carboxylating reagent, in 80oC continues reaction 5 hours, then
Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)2Aqueous suspension
It is neutralized to pH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic
Sour calcium.
Lived in the fatty alcohol polyoxypropylene APEO calcium carboxylates surface of benzyltriethylammoinium chloride and present invention preparation
Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun
Ion：Anionic-nonionic surfactant molar ratio 1: 5 mixes, and obtains surface activator composition 4 c, its composition,
Structure is shown in Table 1 c.
【Embodiment 5c】
By fatty alcohol C10H21OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 10 hours, then adds required oxirane, in 150oC reacts 8 hours again；Then according to fatty alcohol polyoxy
Propylene APEO：ClCH2COONa mol ratio 1：2 addition carboxylating reagent, are then neutralized to pH value with 5wt% aqueous hydrochloric acid solution
For 2, stratification, point removes aqueous phase, oil phase is neutralized to pH value 8 with 10 wt % ammoniacal liquor, vacuum removal moisture obtains anion-non-
Ionic surface active agent fatty alcohol polyoxypropylene APEO carboxylic acid ammonium.
Fatty alcohol polyoxypropylene APEO carboxylic acid ammonium surfactant by tetrabutylammonium chloride and present invention preparation
Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 0.4 mixes, and obtains surface activator composition 5 c, its composition,
Structure is shown in Table 1 c.
【Embodiment 6c】
By fatty alcohol C18H37OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 10 hours, then adds required oxirane, in 160oC reacts 8 hours；Then according to fatty alcohol polyoxypropylene
APEO：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, in 75oC continues reaction 8 hours, then uses 5wt% hydrochloric acid
It is 2 that the aqueous solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8, vacuum with the 10 wt %NaOH aqueous solution
Removing moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.
Fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated surfactant by four octyl group ammonium chlorides and present invention preparation
Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from
Son：Anionic-nonionic surfactant molar ratio 1: 1.6 mixes, and obtains surface activator composition 6 c, its composition,
Structure is shown in Table 1 c.
【Embodiment 7c】
By fatty alcohol C12H23OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 7 hours, then adds required oxirane, in 160oC reacts 5 hours；Then according to fatty alcohol polyoxypropylene
APEO：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, in 80oC continues reaction 8 hours, then uses 5wt% salt
It is 2 that aqueous acid is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)2Aqueous suspension is neutralized to pH
Value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO sulfoacid calcium.
Fatty alcohol polyoxypropylene APEO sulfoacid calcium table by hexadecyltrimethylammonium chloride and present invention preparation
Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 2 mixes, and obtains surface activator composition 7 c, its
Composition, structure are shown in Table 1 c.
【Embodiment 8c】
By fatty alcohol C8H17OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 4 hours, then adds required oxirane, in 160oC reacts 2 hours；Then according to fatty alcohol polyoxypropylene
APEO：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：4 addition sulfonated reagents, in 80oC continues reaction 8 hours, then
Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)2Aqueous suspension
It is neutralized to pH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO sulphur
Sour magnesium.
Fatty alcohol polyoxypropylene APEO sulfonic acid magnesium by dioctadecyl dimethyl ammonium chloride and present invention preparation
Surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 3 mixes, and obtains surface activator composition 8 c,
Its composition, structure are shown in Table 1 c.
【Embodiment 9c】
By fatty alcohol C18H35OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 5 hours, then adds required oxirane, in 160oC reacts 5 hours；Then according to fatty alcohol polyoxypropylene
APEO：Chlorine amyl group sodium sulfonate mol ratio 1：4 addition sulfonated reagents, in 80oC continues reaction 10 hours, then uses 5wt%
It is 2 that aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution,
Vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.
Fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated table by DTAC and present invention preparation
Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant
According to cation：Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, and obtains surface activator composition 9 c,
Its composition, structure are shown in Table 1 c.
【Embodiment 10 c】
By fatty alcohol C18H33OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in
140oC reacts 3 hours, then adds required oxirane, in 160oC reacts 3 hours；Then according to fatty alcohol polyoxypropylene
APEO：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：4 addition sulfonated reagents, in 80oC continues reaction 10 hours, then
Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is neutralized to the 10 wt %NaOH aqueous solution
PH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.
Fatty alcohol polyoxypropylene polyoxyethylene ether sulfonic acid by stearyl dimethyl benzyl ammonium chloride and present invention preparation
Natrium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface-active
Agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains surface activator composition 10
C, its composition, structure are shown in Table 1 c.
【Embodiment 11c】
By the 0.30wt% compound surfactant of embodiment 10c preparation and 0.15wt% polyacrylamide (molecular weight
26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1c surface activator composition composition and structure
【Embodiment 12c】Surface activator composition interface performance is tested
Measure surfactant oil displacement composition and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5-
11 series of strata oil water interfacial tensions.Surface activator composition consumption：0.3 wt %, temperature of the measurement is 81oC, stratum water is NaHCO3
Type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca2+Content 20 mg/L, Mg2+Content 12.2 mg/L.
Table 2c surface activator composition and Shuan He oil field5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 c | 0.0075 |
| 2 c | 0.0062 |
| 3 c | 0.0040 |
| 4 c | 0.0003 |
| 5 c | 0.0075 |
| 6 c | 0.0005 |
| 7 c | 0.0008 |
| 8 c | 0.0054 |
| 9 c | 0.0006 |
| 10 c | 0.0001 |
| 11 c | 0.0008 |
From table 2 c, the compound surfactant of embodiment 1 c～10 c preparation has well for Henan Oil Field
Interface performance.Embodiment 11 c shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still
Well.
The surface activator composition of embodiment 10 c preparation is configured to variable concentrations, respectively test and Shuanghe in Henan's oil
Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3 c.
Table 3c variable concentrations surface activator composition 10 c and Shuanghe Oil Field5-11 series of strata oil water interfacial tension
| Dosage of surfactant (wt%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.005 | 0.003 | 0.002 | 0.0003 | 0.0002 | 0.0001 |
The above results show, compound surfactant composition of the present invention has very high oil for Henan Oil Field crude oil
Water termination activity.
With TX-500C rotating interfacial tensimeter measure again embodiment 8 c preparation compound surfactant with
Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80oC, 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 0.001mN/m, shows this
The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit
Can, have the advantages that the scope of application is wide.
【Embodiment 13 c】Surface activator composition washing oil aptitude tests
Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81oAging 7 days of C, every 2 is little
When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil with the surface activator composition solution of 0.3 wt %
Sand：Solution=1：10 (weight ratios) mix, after aging 48 hours under reservoir temperature, with former in petroleum ether extraction solution
Oil, with 50ml colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activity
Agent solution Central Plains oil concentration.
Table 4c surface activator composition washing oil result
| Embodiment | Washing oil rate % |
| 1 c | 64.0 |
| 2 c | 59.4 |
| 3 c | 55.9 |
| 4 c | 65.1 |
| 5 c | 52.9 |
| 6 c | 60.8 |
| 7 c | 62.3 |
| 8 c | 63.0 |
| 9 c | 64.2 |
| 10 c | 67.6 |
【Embodiment 14 c】Surface activator composition Oil Displacing Capacity is studied
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, the surfactant group of metaideophone 0.3PV (rock pore volume)
After compound, then water drive, to oil-free, improves oil recovery factor and the results are shown in Table 5 c.
Table 5c surface activator composition oil displacement test result
| Embodiment | Improve recovery ratio % |
| 1 c | 6.9 |
| 2 c | 6.2 |
| 3 c | 6.0 |
| 4 c | 8.1 |
| 5 c | 5.3 |
| 6 c | 7.2 |
| 7 c | 8.0 |
| 8 c | 7.4 |
| 9 c | 8.8 |
| 10 c | 10.3 |
Claims (13)
1. compound surfactant composition, including cationic surfactant and Anionic-nonionic surfactant, institute
The mol ratio of the cationic surfactant stated and Anionic-nonionic surfactant is 1: 0.01～1: 100, its middle-jiao yang, function of the spleen and stomach from
Sub- surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant is by following molecule
Formula (A), (B), (C) or (D) represents：
Wherein M is any one in alkali metal, alkaline-earth metal or ammonium root, and R is H, C1～C20Alkyl, C6～C10Aryl or
Any one in substituted aryl, m and n independence value is any one integer or decimal in 0～100；R ' is C1～C10's
Alkylidene；R is M and SO in general molecular formula3Group or the mol ratio of M and COO group, the r=1 when M is for alkali metal or ammonium root,
When M is for alkaline-earth metal, r=0.5；R1For C1～C50Alkyl or alkenyl.
2. according to claim 1 compound surfactant composition it is characterised in that m>0；For general molecular formula (C) and
(D) the optional m further of the Anionic-nonionic surfactant shown in>0 and n>0.
3. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that described cation surface activating
Agent is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
4. according to compound surfactant composition described in claim 1 or 2 it is characterised in that described cationic surfactant
Carbon number in molecule is 4～40.
5. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R is H, C5～C15Alkyl.
6. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R1For C5～C20Alkyl, alkene
Base.
7. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R ' is C1～C5Alkylidene.
8. according to claim 1 compound surfactant composition it is characterised in that m and n is any one in 0～50
Individual integer or decimal.
9. the preparation method of compound surfactant composition described in claim 1, comprises the following steps：
A) by alkyl phenol polyoxyethylene polyoxypropylene ether, catalyst according to mol ratio 1:(1～5) add reactor, room temperature～
100 DEG C alkalize 1～10 hour, then add sulfonated reagent or carboxylating reagent, wherein alkyl phenol polyoxyethylene polyoxypropylene ether：Sulphur
Changing reagent or the mol ratio of carboxylating reagent is 1：(1～4), is warming up to 50～100 DEG C and reacts 1～20 hour, post-treated alkane
Base phenol polyoxyethylene polyoxypropylene ether sulfonate or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylate；Described catalyst is alkali
Property catalyst；Described sulfonated reagent is hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Described carboxylating reagent is halo
Carboxylic acid and its salt；
B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is dissolved separately in
In water, then mix according to mol ratio (1: 0.1)～(1: 10), obtain described surface activator composition.
10. the preparation method of compound surfactant composition according to claim 9, is characterized in that described post processing
Adjust to pH=1～3 including with acidic aqueous solution, carry out water-oil separating, oil phase adds alkali lye to be neutralized to pH=7～9.
The preparation method of 11. compound surfactant compositions according to claim 9, is characterized in that described base catalysis
Agent is alkali metal hydroxide.
12. according to claim 11 compound surfactant composition preparation method, it is characterized in that described alkali metal
Hydroxide is at least one in NaOH or KOH.
Application in tertiary oil recovery for the compound surfactant composition any one of 13. claims 1 to 8.
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| CN201310237545.XA CN104232045B (en) | 2013-06-17 | 2013-06-17 | Composite surface active agent composition and preparation method and application thereof |
| MYPI2015704573A MY180162A (en) | 2013-06-17 | 2014-06-17 | A surfactant composition, production and use thereof |
| MX2015017524A MX2015017524A (en) | 2013-06-17 | 2014-06-17 | Surfactant composition, and manufacturing method and application of same. |
| US14/899,541 US10723936B2 (en) | 2013-06-17 | 2014-06-17 | Surfactant composition, and manufacturing method and application of same |
| PCT/CN2014/000595 WO2014201854A1 (en) | 2013-06-17 | 2014-06-17 | Surfactant composition, and manufacturing method and application of same |
| CA2915832A CA2915832C (en) | 2013-06-17 | 2014-06-17 | Surfactant composition comprising a cationic quaternary ammonium surfactant and an anionic-nonionic surfactant, production and use thereof |
| RU2016101043A RU2647554C2 (en) | 2013-06-17 | 2014-06-17 | Surfactant composition, production and use thereof |
| NO20160047A NO347784B1 (en) | 2013-06-17 | 2016-01-11 | A surfactant composition, production and use thereof |
| US16/899,229 US11578253B2 (en) | 2013-06-17 | 2020-06-11 | Surfactant composition, and manufacturing method and application of same |
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| CN113861049B (en) * | 2021-10-22 | 2024-03-22 | 中国石油化工股份有限公司 | CO (carbon monoxide) 2 Solubilizing viscosity reducer and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN104232045A (en) | 2014-12-24 |
| NO20160047A1 (en) | 2016-01-11 |
| NO347784B1 (en) | 2024-03-25 |
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