CN112225667A - Composite surfactant composition, oil displacement agent, preparation method and application thereof - Google Patents
Composite surfactant composition, oil displacement agent, preparation method and application thereof Download PDFInfo
- Publication number
- CN112225667A CN112225667A CN201910633121.2A CN201910633121A CN112225667A CN 112225667 A CN112225667 A CN 112225667A CN 201910633121 A CN201910633121 A CN 201910633121A CN 112225667 A CN112225667 A CN 112225667A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- alkali metal
- oil
- mol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 193
- 239000000203 mixture Substances 0.000 title claims abstract description 155
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 title claims description 94
- 239000003921 oil Substances 0.000 claims abstract description 132
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 125
- 150000003839 salts Chemical class 0.000 claims abstract description 107
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 55
- 229920000570 polyether Polymers 0.000 claims abstract description 55
- 239000010779 crude oil Substances 0.000 claims abstract description 51
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 13
- -1 alkylene carboxylates Chemical class 0.000 claims description 185
- 238000006243 chemical reaction Methods 0.000 claims description 179
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 107
- 239000000243 solution Substances 0.000 claims description 73
- 238000010992 reflux Methods 0.000 claims description 72
- 239000007864 aqueous solution Substances 0.000 claims description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 39
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 23
- 238000011084 recovery Methods 0.000 claims description 23
- 229920002401 polyacrylamide Polymers 0.000 claims description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- 230000002209 hydrophobic effect Effects 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 229940106681 chloroacetic acid Drugs 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 7
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000008398 formation water Substances 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- FXKMTSIKHBYZSZ-UHFFFAOYSA-N 2-chloroethanesulfonic acid Chemical compound OS(=O)(=O)CCCl FXKMTSIKHBYZSZ-UHFFFAOYSA-N 0.000 claims description 4
- DDLBHIIDBLGOTE-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid Chemical compound ClCC(O)CS(O)(=O)=O DDLBHIIDBLGOTE-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 238000005956 quaternization reaction Methods 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical group 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 33
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 120
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 56
- 238000003756 stirring Methods 0.000 description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 47
- 238000001816 cooling Methods 0.000 description 46
- 229920001451 polypropylene glycol Polymers 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 35
- 238000002474 experimental method Methods 0.000 description 32
- 239000012071 phase Substances 0.000 description 32
- 239000000126 substance Substances 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 28
- 230000003068 static effect Effects 0.000 description 20
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- QRRQPVYWGVIEOH-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC[N+](C)(CC([O-])=O)C1=CC=CC=C1 Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(CC([O-])=O)C1=CC=CC=C1 QRRQPVYWGVIEOH-UHFFFAOYSA-N 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 17
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 16
- 238000010907 mechanical stirring Methods 0.000 description 16
- 230000018044 dehydration Effects 0.000 description 15
- 238000006297 dehydration reaction Methods 0.000 description 15
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000005063 solubilization Methods 0.000 description 12
- 230000007928 solubilization Effects 0.000 description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 229960003237 betaine Drugs 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 8
- WEMFIGZASIEGGG-UHFFFAOYSA-N 2-[dimethyl(phenyl)azaniumyl]acetate Chemical compound [O-]C(=O)C[N+](C)(C)C1=CC=CC=C1 WEMFIGZASIEGGG-UHFFFAOYSA-N 0.000 description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- PPHQUIPUBYPZLD-UHFFFAOYSA-N n-ethyl-n-methylaniline Chemical compound CCN(C)C1=CC=CC=C1 PPHQUIPUBYPZLD-UHFFFAOYSA-N 0.000 description 8
- 230000003381 solubilizing effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 6
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 6
- LPMRQMCFYNYYBF-UHFFFAOYSA-N CCCCCCCCCCCCCCCCC(C=C1)=CC=C1[N+](C)(C)CC([O-])=O Chemical compound CCCCCCCCCCCCCCCCC(C=C1)=CC=C1[N+](C)(C)CC([O-])=O LPMRQMCFYNYYBF-UHFFFAOYSA-N 0.000 description 6
- QBLDLGLDZKWQAU-UHFFFAOYSA-N CCCCCCCCCCCC[N+](C)(CC([O-])=O)C1=CC=CC=C1 Chemical compound CCCCCCCCCCCC[N+](C)(CC([O-])=O)C1=CC=CC=C1 QBLDLGLDZKWQAU-UHFFFAOYSA-N 0.000 description 6
- KXBMNUAFIQLKHL-UHFFFAOYSA-N CCCCCCCCCCCC[N+](CCOCC(O)=O)(CC([O-])=O)C1=CC=CC=C1 Chemical compound CCCCCCCCCCCC[N+](CCOCC(O)=O)(CC([O-])=O)C1=CC=CC=C1 KXBMNUAFIQLKHL-UHFFFAOYSA-N 0.000 description 6
- UBIQNBAACDVDEE-UHFFFAOYSA-N CC[N+](CC)(CC([O-])=O)C1=CC=CC=C1 Chemical compound CC[N+](CC)(CC([O-])=O)C1=CC=CC=C1 UBIQNBAACDVDEE-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002888 zwitterionic surfactant Substances 0.000 description 5
- GKQIPHZCJYELEN-UHFFFAOYSA-N 2-(N-dodecylanilino)ethanol Chemical compound OCCN(C1=CC=CC=C1)CCCCCCCCCCCC GKQIPHZCJYELEN-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- GYCIMNXULSVHHH-UHFFFAOYSA-N 2-hexadecan-4-yl-N,N-dimethylaniline Chemical compound CN(C1=C(C=CC=C1)C(CCC)CCCCCCCCCCCC)C GYCIMNXULSVHHH-UHFFFAOYSA-N 0.000 description 4
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- JGDMUKQCARCGFC-UHFFFAOYSA-N N-hexadecyl-N,4-dimethylaniline Chemical compound CCCCCCCCCCCCCCCCN(C)C1=CC=C(C)C=C1 JGDMUKQCARCGFC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- GOJIVVWJAXAPGS-UHFFFAOYSA-N n-dodecyl-n-methylaniline Chemical compound CCCCCCCCCCCCN(C)C1=CC=CC=C1 GOJIVVWJAXAPGS-UHFFFAOYSA-N 0.000 description 4
- SURXVYKTTZVULC-UHFFFAOYSA-N n-methyl-n-octadecylaniline Chemical compound CCCCCCCCCCCCCCCCCCN(C)C1=CC=CC=C1 SURXVYKTTZVULC-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- AVBGNFCMKJOFIN-UHFFFAOYSA-N triethylammonium acetate Chemical compound CC(O)=O.CCN(CC)CC AVBGNFCMKJOFIN-UHFFFAOYSA-N 0.000 description 4
- MPLIJWMZXSTSDQ-UHFFFAOYSA-N 2-(prop-2-enoylamino)dodecane-1-sulfonic acid Chemical group CCCCCCCCCCC(CS(O)(=O)=O)NC(=O)C=C MPLIJWMZXSTSDQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- HTYRTGGIOAMLRR-UHFFFAOYSA-N 5-amino-4-hydroxybenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O HTYRTGGIOAMLRR-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OWBRWDRADNPYKD-UHFFFAOYSA-N CC[N+](C)(CC([O-])=O)C1=CC=CC=C1 Chemical compound CC[N+](C)(CC([O-])=O)C1=CC=CC=C1 OWBRWDRADNPYKD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- HDSLCWKGMZURQW-UHFFFAOYSA-N n,n-diethylethanamine;dodecane-1-sulfonic acid Chemical compound CCN(CC)CC.CCCCCCCCCCCCS(O)(=O)=O HDSLCWKGMZURQW-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- VODRWDBLLGYRJT-UHFFFAOYSA-N propan-2-yl 2-chloroacetate Chemical compound CC(C)OC(=O)CCl VODRWDBLLGYRJT-UHFFFAOYSA-N 0.000 description 2
- ISYUCUGTDNJIHV-UHFFFAOYSA-N propyl 2-bromoacetate Chemical compound CCCOC(=O)CBr ISYUCUGTDNJIHV-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- XOQMWEWYWXJOAN-UHFFFAOYSA-N 3-methyl-3-(prop-2-enoylamino)butanoic acid Chemical compound OC(=O)CC(C)(C)NC(=O)C=C XOQMWEWYWXJOAN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical class OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000008384 inner phase Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- FIJPWGLOBMXXSF-UHFFFAOYSA-M potassium;2-hydroxyacetate Chemical compound [K+].OCC([O-])=O FIJPWGLOBMXXSF-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- QDFJZFOEPUNIDI-UHFFFAOYSA-M sodium;1-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].CC(O)C(Cl)S([O-])(=O)=O QDFJZFOEPUNIDI-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
- C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a composite surfactant composition, a preparation method and application thereof, and mainly solves the problems that the existing surfactant has low oil displacement efficiency, poor temperature resistance and salt resistance and large adsorption retention capacity and cannot meet the oil displacement requirement of an oil reservoir. The invention better solves the problem by adopting the technical scheme that the composite surfactant composition comprises the zwitterionic compound shown in the formula (I), the surfactant shown in the formula (II) and containing polyether segments or not containing polyether segments, and at least one of small molecular alcohol or amine, salt and inorganic base, and can be used for improving the yield of crude oil in oil fields.
Description
Technical Field
The invention relates to a composite surfactant composition, an oil displacement agent, a preparation method and application thereof.
Background
The enhanced oil recovery technology, namely the Enhanced Oil Recovery (EOR) and Improved Oil Recovery (IOR) technology generally referred to abroad, can be summarized into six aspects of improving water flooding, chemical flooding, heavy oil thermal recovery, gas flooding, microbial oil recovery, physical oil recovery and the like. Currently, the enhanced oil recovery techniques that enter large-scale applications in mines are concentrated in three major categories, thermal recovery, gas flooding and chemical flooding. Chemical flooding is a strengthening measure for improving the recovery ratio by adding a chemical agent into an aqueous solution and changing the physicochemical property and rheological property of an injected fluid and the interaction characteristic with reservoir rocks, and is rapidly developed in China, mainly because the reservoir deposits in China have strong heterogeneity, the viscosity of the continental-phase crude oil is high, and the method is more suitable for chemical flooding in an EOR method.
Surfactants as an important component of chemical flooding can be classified into two major classes, namely ionic and nonionic, according to their chemical composition and molecular structure. The most anionic surfactant types are currently used in tertiary oil recovery studies, followed by nonionic and zwitterionic surfactants, and the least cationic surfactant is used. The results of oil displacement by using alkaline water, surfactant or alkaline water oil displacement and oil displacement by using zwitterionic surfactant are sequentially reported by US3927716, US4018281 and US4216097 of Mofu Petroleum company, the zwitterionic surfactant is carboxylic acid or sulfonate type betaine surfactant with different chain lengths, and the interfacial tension on crude oil in Texas south Texas is 10 in simulated saline with total mineralization of 62000-160000 mg/L and calcium and magnesium ions of 1500-18000 mg/L-1～10-4mN/m. For example, chinese patents CN 1528853, CN 1817431, CN 1066137 and the like sequentially report bisamide type cationic, fluorine-containing cationic and pyridyl-containing cationic gemini surfactants, but the use of cations in oil fields is limited due to the disadvantages of large adsorption loss, high cost and the like.
After the surfactants of different types are compounded with each other, the defects of a single surfactant can be overcome, and the advantages of each component are exerted, so that the composite surfactant composition has more excellent performance. Chinese patent CN1458219A discloses a surfactant/polymer binary ultra-low interfacial tension composite flooding formula for tertiary oil recovery, wherein the used surfactant is petroleum sulfonate or a composite surfactant composition compounded by petroleum sulfonate serving as a main agent, a diluent and other surfactants, the weight percentage of the components is 50-100% of petroleum sulfonate, 0-50% of alkyl sulfonate, 0-50% of carboxylate, 0-35% of alkyl aryl sulfonate and 0-20% of low-carbon alcohol, and the surfactant system is too complex. The United states Texas university patent US8211837 reports that branched long carbon alcohol is obtained by catalytic dimerization reaction of simple and cheap linear alcohol at high temperature, the branched long carbon alcohol is polymerized with propylene oxide and ethylene oxide and then is subjected to sulfuric acid esterification reaction, compared with an expensive sulfonate surfactant, a large hydrophilic group polyether sulfate surfactant is synthesized at low cost, the sulfate surfactant has excellent high-temperature stability under an alkaline condition due to the existence of large hydrophilic groups, 0.3 percent of branched alcohol polyether sulfate (C32-7PO-6EO sulfate) and 0.3 percent of internal olefin sulfonate (C20-24 IOS) saline solution are mixed with the same amount of crude oil at 85 ℃, and the solubilization parameter is 14. Patent US4370243 of meifu petroleum company reports an oil displacement system composed of oil-soluble alcohol, betaine sulfonate and quaternary ammonium salt, which can function as both a surfactant and a fluidity control agent, wherein the quaternary ammonium salt is a cationic surfactant with a lipophilic carbon chain length of 16-20, 2% octadecyl dihydroxyethyl propyl betaine sulfonate and 1.0% hexanol are used as oil displacement agents, after 1.9PV is injected, the crude oil can be 100% displaced, but the adsorption loss of the surfactant is as large as 6mg/g, and 2.0% tetraethylammonium bromide with a relatively low price is added as a sacrificial agent to reduce the adsorption capacity of the surfactant.
Research results at home and abroad show that the surfactant is limited in practical application as an oil displacement agent due to large use amount, high preparation cost and poor use effect of a single surfactant. The invention relates to a composite surfactant composition with stable structure under oil reservoir conditions, an oil displacement agent, a preparation method and application thereof.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the surfactant which is mainly composed of an oil displacement agent system in the prior art has poor crude oil solubilization capacity, low oil displacement efficiency, poor temperature resistance and salt resistance, and large adsorption retention capacity, and cannot meet the requirements of high-temperature and high-salt oilThe problem of reservoir oil displacement needs is solved, and a novel composite surfactant composition is provided. The aqueous solution of the composite surfactant composition can well emulsify crude oil, has strong solubilizing capability and the maximum solubilizing parameter of 17.9-23.7, thereby effectively improving the oil displacement efficiency of the crude oil, having good application prospect of improving the recovery ratio and good performance of reducing the interfacial tension, and the oil-water interfacial tension can reach 10-3～10-4mN/m。
The second technical problem to be solved by the present invention is to provide a method for preparing a composite surfactant composition corresponding to the solution of the first technical problem.
The invention also provides application of the composite surfactant composition corresponding to the solution of one of the technical problems.
The fourth technical problem to be solved by the invention is that the oil displacement agent system containing the surfactant in the prior art has the problems of poor crude oil compatibilization capacity, low oil displacement efficiency, poor temperature and salt resistance, large adsorption retention and incapability of meeting the oil displacement requirement of a high-temperature and high-salt reservoir, and the invention provides a novel oil displacement agent, so that the aqueous solution of the oil displacement agent can well emulsify the crude oil, has stronger solubilization capacity, the maximum solubilization parameter is 17.9-23.7, thereby effectively improving the oil displacement efficiency, having good application prospect of improving the oil recovery ratio, having good performance of reducing the interfacial tension, and the oil-water interfacial tension can reach 10-3～10-4mN/m。
The fifth technical problem to be solved by the present invention is to provide a method for preparing an oil displacement agent corresponding to the fourth technical problem to be solved.
The sixth technical problem to be solved by the present invention is to provide an application of the oil displacement agent corresponding to the fourth technical problem to be solved.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a composite surfactant composition comprising the following components:
(1) a zwitterionic compound;
(2) a surfactant containing polyether segments or no polyether segments;
wherein the molar ratio of the zwitterionic compound to the surfactant containing polyether or no polyether segment is (1:0.02) - (1: 20); the molecular general formula of the zwitterionic compound is shown as the formula (I):
in the formula (I), R1And R4Is hydrogen, C2～C32Alkyl or substituted alkyl of (CH R')cOH、(CH R')dCH3One of phenyl, substituted phenyl or benzyl, R2Y-Is C1～C5Alkylene or substituted alkylene carboxylates, C1～C5Alkyl or substituted alkyl sulfonates, C1～C5Hydrocarbyl or substituted hydrocarbyl phosphate or C1～C5At least one of hydrocarbyl or substituted hydrocarbyl sulfate, R3Is hydrogen, C2～C32Alkyl or substituted alkyl (CHR')eOH, halogen, amino, carboxylic acid group or sulfonic group, R 'and R' are independently selected from H, CH3Or C2H5C is any integer of 1 to 4, d is any integer of 0 to 5, and e is any integer of 0 to 4.
The molecular general formula of the surfactant containing polyether segments or not containing polyether segments is as follows:
in the formula (II), R5Is C8～C30Or one of a substituted hydrocarbon group or C4～C20A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R5O is abietate; m1 and m2 are the addition number of ethoxy groups, m1 is 0-50, and m2 is 0-50; n is the addition number of the propoxy groups, and n is 0-100; k is 0 or 1; when k is 1, X is hydrogen or R5Z，R5Is C1～C5Z is COOM, SO3N or hydrogen, M, N is selected from hydrogen ion, cation or cation group; when k is 0, X is COOM or SO3And one of N, M, N is selected from hydrogen ion, cation or cation group.
In the above technical scheme, R1Or R4Preferably hydrogen, C8～C24The alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl.
In the above technical scheme, R2Y-Preferably C1～C3Alkylene or substituted alkylene carboxylates, C1～C3One of alkyl or substituted alkyl sulfonate.
In the above technical scheme, R3Preferably hydrogen, C8～C24Hydrogen, methyl, ethyl, phenyl, hydroxyl, amino, carboxylic acid or sulfonic acid.
In the above technical scheme, R', R0Preferably H or CH3。
In the above technical means, c is preferably 1 to 2, d is preferably 0 to 1, and e is preferably 0 to 1.
In the above embodiments, M, N is preferably a hydrogen ion, an alkali metal cation, or a compound represented by the formula NR7(R8)(R9)(R10) At least one of the groups shown.
In the above technical scheme, R7、R8、R9、R10Preferably H, (CHR)0)fOH or (CHR)0)gCH3One kind of (1).
In the above technical scheme, R0Preferably H, CH3Or C2H5One kind of (1).
In the above-described embodiment, f is preferably 1 to 2, and g is preferably 0 to 1.
In the above-described embodiment, j is preferably 0 or 1
In the above technical scheme, R5Preferably C12～C24Or with a hydrocarbon or substituted hydrocarbon radical of4～C20Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)6H5C(CH3)2) Substituted benzene or naphthalene rings, or R5O is abietate.
In the above technical scheme, R6Preferably C1～C3Alkylene or hydrogen.
In the above technical solution, preferably, m1 is 0 to 10, m2 is 0 to 10, and n is 0 to 20.
In the above technical solution, the composite surfactant composition preferably further comprises the following components:
(3) a small molecule alcohol;
(4) a small molecule amine;
(5) salt;
(6) an inorganic base;
wherein the molar ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the inorganic base is 1 (0.05-20): 0-10; the small molecular alcohol is selected from C1～C8The fatty alcohol of (a); the small molecule amine is selected from C1～C8At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is at least one selected from alkali metal hydroxide, alkali metal carbonate or alkali metal bicarbonate.
In the technical scheme, the molar preferred ratio of the zwitterionic compound, the surfactant containing polyether segments or not containing polyether segments, the small molecular alcohol, the small molecular amine, the salt and the inorganic base is 1 (0.2-20): 0-15): 0-5.
In the above technical scheme, the preferable small molecular alcohol is C1～C5The fatty alcohol of (1).
In the above technical scheme, the preferable small molecule amine is C1～C5The fatty amine of (1).
In the above technical solution, the metal halide is preferably an alkali metal halide, and is further preferably one of sodium chloride, potassium chloride, sodium bromide and potassium bromide; the hydroxyl-substituted carboxylate is preferably one of sodium glycolate and potassium glycolate.
In the above technical solution, the inorganic base is preferably an alkali metal hydroxide, carbonate or bicarbonate.
An N, N-disubstituted aniline compound represented by the formula (I) in the absence of an ionization reaction
Can be obtained from commercial sources or synthesized by conventional techniques in the art.
The composite surfactant composition for oil displacement can also comprise oil displacement components commonly used in the field, such as an oil displacement polymer, an oil displacement foaming agent, oil displacement mineral substances (such as sodium chloride and potassium chloride), alkaline substances (such as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine, triethanolamine and other micromolecular organic amines), and organic micromolecular auxiliaries comprise short-chain fatty alcohol, low-carbon-chain ketone, DMSO and the like.
The key effective components of the compound oil-displacing surfactant are (1) and (2), and a person skilled in the art knows that the compound oil-displacing surfactant can be supplied in various forms for transportation, storage or field use, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form; the aqueous solution form comprises a form of preparing a concentrated solution by water and a form of directly preparing a solution with concentration required by on-site oil displacement, for example, a solution with the key active ingredient content of 0.005-0.6 wt% by weight is a form suitable for on-site oil displacement; the water is not particularly required, and can be deionized water or water containing inorganic mineral substances, and the water containing the inorganic mineral substances can be tap water, oil field formation water or oil field injection water.
To solve the second technical problem, the technical solution adopted by the present invention is as follows: the preparation method of the composite surfactant composition in one of the technical problems comprises the following steps:
(a) preparation of zwitterionic compound:
will be provided with
With ionizing agents R2Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain a water solution or an alcohol water solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C1～C5The fatty alcohol of (a);
(b) preparation of the composite surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;
wherein the surfactant with the structure shown in the formula (II) is prepared by adopting the following method optionally:
in the presence of an alkaline catalyst, R5OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a polyether compound; mixing a required amount of polyether compound with the aqueous solution or the aqueous solution of the compound containing the aniline structure obtained in the step (a) to obtain the surfactant composition for oil displacement; or obtaining the surfactant composition for oil displacement through a second reaction:
② the polyether compound obtained in the step I and an ionizing agent Y0R6Mixing Z and alkali metal hydroxide or alkali metal alkoxide according to a molar ratio of 1 (0.1-20) to 0.1-20, reacting for 3-15 hours at a reaction temperature of 50-120 ℃ under stirring, adding the aqueous solution containing the aniline structure compound or the small molecular alcohol aqueous solution obtained in the step (a) according to a required molar ratio, heating to 40-100 ℃, and stirring for 1-5 hours to obtain the required surfactant composition for oil displacement; wherein, Y0Selected from chlorine, bromine or iodine;
or: ② the polyether compound obtained in the step I and an ionizing agent Y0R6 Z0And alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1: (0.1-20), reacting at 50-120 ℃ for 3-15 hours under stirring, continuously adding water for saponification, refluxing for 1-10 hours, adding the aqueous solution containing the aniline structure compound or the small molecular alcohol aqueous solution obtained in the step (a) according to the required molar ratio, heating to 40-100 ℃, and stirring for 1-5 hours to obtain the required surfactant composition; wherein Z is0Is selected from COOR0,R0Is selected from C1～C8Alkyl group of (1).
In the above technical scheme, the surfactant having the structure shown in formula (II) is not limited to the above preparation method, and may be commercially available.
In the above technical scheme, the ionizing agent R in the step (a)2Y is preferably at least one of an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid, and an alkali metal salt of chloroacetic acid.
In the above technical scheme, the small molecule alcohol in the step (a) is preferably C1～C4The fatty alcohol of (1).
In the above technical scheme, in the step (a)
And R2The preferred molar ratio of Y is 1: 1-3.
In the above technical scheme, the reaction temperature in the step (b) is preferably 120 to 160 ℃, the basic catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate, and the pressure is preferably 0.30 to 0.60MPa gauge pressure.
In the above technical solution, the alkali metal hydroxide in the step (b) is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (0.3-3) to (0.2-6), and R is0Preferably C1～C4Alkyl group of (1).
Y0R6Examples of Z include, but are not limited to, chloroacetic acid, sodium chloroacetate, sodium 1-chloro-2-hydroxypropanesulfonate, and the like.
Y0R6Z0Examples of (d) are, but not limited to, chloroacetates (e.g., ethyl chloroacetate), bromoacetates (e.g., ethyl bromoacetate), and the like.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the composite surfactant composition in the technical scheme in oil displacement of oil fields.
In the technical scheme, the composite surfactant composition can be applied according to the prior art, can be used independently, and can also be compounded with common oil field auxiliaries for use; as a preferable scheme: the total salinity of stratum saline water of the oil reservoir is preferably selected from 5000-200000 mg/L in the application, wherein Ca is2++Mg2+10 to 15000mg/L, HCO 3 -0 to 2000 mg/L; the viscosity of the crude oil is 1.0-200.0 mPa.s; the formation temperature is 50-120 ℃.
The composite surfactant composition prepared by the invention shows synergistic interaction among the components in the aspects of increasing the surface activity, reducing the critical micelle concentration, improving the crude oil solubilizing capability and the like. Especially, the electrostatic effect of the surfactants with opposite electric properties promotes the association between two kinds of surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the two have certain hydrophobic effect to promote different surfactant molecules to adopt a tighter arrangement mode, so that micelles are easily formed in a solution, and higher surface activity and lower critical micelle concentration than a single surfactant are generated. In addition, the preparation method of the composite surfactant composition adopted by the invention has the advantages that the high-purity ionic surfactant is high in price and can be obtained only by complex purification steps such as extraction, column chromatography and the like, so that the preparation cost of the surfactant for oil displacement is greatly increased. Polyether and halogenated carboxylate or halogenated carboxylate are adopted to generate polyether carboxylate or polyether carboxylate under the catalysis of alkali metal hydroxide or alkali metal alkoxide, the polyether carboxylate is obtained without separation or direct saponification, a required amount of zwitterionic compound water or small molecular alcohol aqueous solution is added for mixing, small molecular alcohol or amine in a system and a surfactant can form a composite membrane at an interface and are distributed to an oil phase and an aqueous phase, the properties of the oil phase and the aqueous phase are improved, the oil phase and the aqueous phase are favorably reduced in tension and formed in microemulsion, and the generated inorganic salt has a promoting effect on the interface performance and does not need to be removed, the excessive alkali metal hydroxide can neutralize acid substances in the crude oil to form soap, so that the solubilizing capability of the surfactant on the crude oil is further improved, the oil washing efficiency of the composite surfactant composition is improved, and the green production of the surfactant is realized.
The present invention refers to the total concentration of the components of the molecular formula (I) and the molecular formula (II) in the above technical scheme, when the content or concentration of the surfactant composition is referred to.
In order to solve the fourth technical problem, the invention adopts the technical scheme that: the composite oil displacement agent comprises the following components in parts by weight:
(1)1 part of the surfactant composition according to any one of claims 1 to 4 or the surfactant composition prepared by the preparation method according to any one of claims 5 to 6;
(2)0 to 20 parts of a polymer and more than 0 part of a polymer;
(3) 0-30 parts of alkali.
In the above technical solution, the polymer is not strictly limited, and may be various polymers for oil field oil recovery known to those skilled in the art, such as but not limited to at least one selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anionic polyacrylamide, temperature-resistant and salt-resistant modified polyacrylamide, hydrophobically associating polymer, and polymer microspheres.
In the technical scheme, the preferable molecular chain of the temperature-resistant and salt-resistant modified polyacrylamide comprises an acrylamide structural unit and a temperature-resistant and salt-resistant monomer structural unit, the molar ratio of the acrylamide structural unit to the temperature-resistant and salt-resistant monomer structural unit is (0.1-40) to 1, the viscosity average molecular weight is 800-2500 ten thousand, and further, the preferable molecular chain of the temperature-resistant and salt-resistant monomer is 2-acrylamido-2-methylpropanesulfonic acid; the molecular chain of the hydrophobic association polymer comprises an acrylamide structural unit, a temperature-resistant and salt-resistant monomer structural unit and a hydrophobic monomer structural unit, wherein the molar ratio of the acrylamide structural unit to the temperature-resistant and salt-resistant monomer structural unit to the hydrophobic monomer structural unit is 1: (0.1-40): (0.001 to 0.05) and a viscosity average molecular weight of 500 to 2500 ten thousand.
In the technical scheme, the hydrophobic association polymer is preferably copolymerized by acrylamide, a temperature-resistant salt-resistant monomer or a hydrophobic monomer; the temperature-resistant and salt-resistant modified polyacrylamide is preferably copolymerized by acrylamide and a temperature-resistant and salt-resistant monomer; the temperature-resistant and salt-resistant monomer or hydrophobic monomer may be at least one of monomers having a large side group or a rigid side group (e.g., styrenesulfonic acid, N-alkylmaleimide, acrylamido long-chain alkylsulfonic acid, long-chain alkylallyl dimethylammonium halide, 3-acrylamido-3-methylbutyric acid, etc.), monomers having a salt-resistant group (e.g., 2-acrylamido-2-methylpropanesulfonic acid), monomers having a hydrolysis-resistant group (e.g., N-alkylacrylamide), monomers having a group that inhibits hydrolysis of an amide group (e.g., N-vinylpyrrolidone), monomers having a hydrophobic group, etc.), which are well known to those skilled in the art, the temperature-resistant and salt-resistant monomer is preferably 2-acrylamido-2-methylpropanesulfonic acid, and the hydrophobic monomer is preferably 2-acrylamidododecyl sulfonic acid.
In the above technical scheme, the mole ratio of acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer in the hydrophobic association polymer is preferably 1: (0.1-40): (0.001 to 0.05) and a viscosity average molecular weight of 500 to 2500 ten thousand; more preferably, the molar ratio of the acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer is 1 to (0.1-20) to (0.001-0.01), and the viscosity average molecular weight is 1200-2200 ten thousand.
In the technical scheme, the molar preferred ratio of the acrylamide to the temperature-resistant salt-resistant monomer in the temperature-resistant salt-resistant modified polyacrylamide is (0.1-40) to 1.
In the above technical scheme, the hydrophobic association polymer is preferably formed by copolymerizing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid, and the molar ratio of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid is preferably 1: (0.1-40): (0.001 to 0.05), more preferably 1: (0.1 to 20): (0.001 to 0.01).
In the technical scheme, the temperature-resistant salt-resistant modified polyacrylamide is preferably prepared by copolymerizing acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, the molar ratio of the acrylamide to the 2-acrylamide-2-methylpropanesulfonic acid is preferably (0.1-40): 1, and the viscosity average molecular weight of the modified polyacrylamide is preferably 800-2500 ten thousand.
In the above technical scheme, the alkali is an inorganic alkaline substance or an organic alkali.
In the above technical solution, the inorganic basic substance is preferably at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, and an alkali metal carbonate; it is further preferable that the alkali metal hydroxide is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide, the alkaline earth metal hydroxide is at least one selected from the group consisting of magnesium hydroxide and calcium hydroxide, and the alkali metal carbonate is at least one selected from the group consisting of sodium carbonate and sodium bicarbonate.
In the above technical solution, the organic base preferably contains at least one of a primary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium base in a molecule, and more preferably C1～C8At least one of short carbon chain organic amines, more preferably at least one of ethanolamine, diethanolamine, triethanolamine or triethylamine.
In the technical scheme, the mass ratio of the surfactant composition to the polymer to the alkali in the composite oil displacement agent is preferably 1 to (0.1-2): (0-5).
The key active ingredients of the oil-displacing agent composition of the present invention are the components 1), 2) and 3), and those skilled in the art know that various supply forms such as a non-aqueous solid form, an aqueous paste form, or an aqueous solution form can be adopted for convenience of transportation and storage or field use; the water solution form comprises a form of preparing a concentrated solution by using water and a form of directly preparing an oil displacement agent with the concentration required by on-site oil displacement; the water is not particularly required, and can be deionized water or water containing inorganic mineral substances, and the water containing the inorganic mineral substances can be tap water, oil field formation water or oil field injection water.
The oil displacement agent composition of the present invention may further contain oil recovery aids such as a foaming agent, small molecular organic substances (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, DMSO, etc.) and the like which are commonly used in the art.
In order to solve the fifth technical problem, the invention adopts the technical scheme that: a preparation method of the composite oil displacement agent according to any one of the four technical solutions to solve the technical problems, comprising the following steps:
(a) preparation of zwitterionic compound:
will be provided with
With ionizing agents R2Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain a water solution or an alcohol water solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C1～C5The fatty alcohol of (a);
(b) preparation of surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;
wherein the surfactant with the structure shown in the formula (II) is prepared by adopting the following method optionally:
in the presence of an alkaline catalyst, R5OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); (ii) a Or further reacting through an optional step (II) to obtain the ionic polyether compound with the structure shown in the formula (II):
② the polyether compound obtained in the step I and an ionizing agentY0R6Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, and the mixture is stirred and reacted for 3-15 hours at the reaction temperature of 50-120 ℃ to obtain the ionic polyether compound; wherein, Y0Selected from chlorine, bromine or iodine;
or: ② the polyether compound obtained in the step I and an ionizing agent Y0R6Z0And alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, the mixture is stirred and reacted for 3-15 hours at the reaction temperature of 50-120 ℃, water is continuously added for saponification reaction, and the ionic polyether compound is obtained after refluxing for 1-10 hours; wherein, Y0Selected from chlorine, bromine or iodine, Z0Is selected from COOR0,R0Is selected from C1～C8Alkyl groups of (a);
(c) and (b) uniformly mixing the surfactant composition obtained in the step (b) with a polymer and alkali according to the required amount by mass to obtain the composite oil-displacing agent.
In the above technical solution, the preferable solution is: the ionizing agent R2Y is preferably at least one of an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid, and an alkali metal salt of chloroacetic acid sulfonating agent, and the alcohol is preferably selected from C1～C4The fatty alcohol of (a); the above-mentioned
And R2The preferred molar ratio of Y is 1: 1-3; the method comprises the following steps: the reaction temperature is preferably 120-160 ℃, the pressure is preferably 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate; the second step is as follows: the alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (0.3-3) to (0.2-6), and Y is preferably 10Preferably one of chlorine or bromine, R0Preferably C1～C4Alkyl group of (1).
In order to solve the sixth technical problem, the invention adopts the technical scheme that: a method for enhanced oil recovery comprising the steps of:
(1) mixing the composite oil displacement agent in any one of the four technical schemes for solving the technical problems with water to obtain an oil displacement system;
(2) and contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-150 ℃ and the total salinity is more than 500 mg/L of simulated formation water, and displacing the crude oil in the oil-bearing stratum.
In the technical scheme, the compound oil-displacing agent can be obtained by mixing the components according to required amount by adopting various conventional mixing methods, and is dissolved by water according to required concentration when used for displacing oil to obtain the oil-displacing agent for displacing oil; and according to the concentration of the required composite oil-displacing agent, respectively dissolving the components in the composite oil-displacing agent in water to obtain the composite oil-displacing agent for oil displacement. The water used in the preparation can be tap water, river water, seawater and oil field formation water.
In the technical scheme, the composite oil displacement agent can be applied according to the prior art, can be used independently, and can also be compounded with an oil field common auxiliary agent for use; as a preferable scheme: the total salinity of stratum saline water of the oil reservoir is preferably selected from 5000-200000 mg/L in the application, wherein Ca is2++Mg2+10 to 15000mg/L, HCO 3 -0 to 2000 mg/L; the viscosity of the crude oil is 1.0-200.0 mPa.s; the formation temperature is 50-120 ℃.
The composite oil displacement agent disclosed by the invention has various advantages of the composite surfactant, and the modified polyacrylamide or the hydrophobically associating polyacrylamide endows the polymer with better temperature resistance and salt resistance due to the introduction of the temperature resistance and salt resistance segments. Alkali in the oil displacement agent can also form soap with a surfactant in crude oil, so that the interfacial activity of an oil displacement system is further improved, the adsorption of the surfactant on a stratum is reduced, and the oil displacement agent has a good effect of improving the recovery ratio of the crude oil.
The invention adopts a physical simulation displacement evaluation method to evaluate the effect, and the specific evaluation method comprises the following steps: drying the core at constant temperature to constant weight, and measuring the gas logging permeability of the core; calculating the pore volume of the simulated oil field stratum water saturated core, recording the volume of saturated crude oil by using the crude oil saturated core at the oil displacement temperature, pumping the stratum water at the speed of 0.2mL/min, driving until the water content reaches 100%, calculating the recovery ratio of the crude oil improved by water drive, then transferring the oil displacement agent obtained in the step (c) at the speed of 0.15mL/min, driving the oil displacement agent to the water content of 100% at the speed of 0.2mL/min, and calculating the percentage of the recovery ratio of the crude oil improved on the basis of the water drive.
The method for testing the interfacial tension comprises the following steps: (1) presetting the temperature to the temperature required by the measurement, and waiting for the temperature to be stable; (2) injecting external phase liquid, filling the centrifuge tube, injecting internal phase liquid, removing bubbles, and tightly covering; (3) the centrifuge tube is arranged in a rotating shaft of the instrument, the rotating speed is set, and a microscope is adjusted to enable inner phase liquid drops or bubbles in the visual field to be very clear; (4) reading and calculating, and calculating the interfacial tension according to the formula (1):
γ＝0.25ω2r3Δ ρ (L/D ≧ 4) formula (1);
wherein γ is the interfacial tension (mN. m)-1) Δ ρ is the two-phase density difference (Kg. m)-3ω is angular velocity (rad · s)-1) R is the minor axis radius (m) of the droplet, L is the major axis (centrifuge tube axial) diameter, and D is the minor axis (centrifuge tube radial) diameter.
The method for testing the static adsorption capacity comprises the following steps: fully mixing a simulated saline solution of a surfactant and an adsorbate according to a certain liquid-solid ratio, oscillating for a certain time at a set temperature and frequency, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant, and calculating the adsorption capacity of the surfactant, wherein the formula (2) is shown:
Γ ═ W (Co × a-Ce)/m formula (2);
wherein gamma is static adsorption capacity (mg/g), W is weight (g) of the surfactant solution, Co is initial concentration (mg/g) of the surfactant solution calculated according to commodity content, A is effective content (%) of the surfactant product, effective concentration (mg/g) of the Ce surfactant solution after adsorption, and m is mass (g) of the adsorbent.
The test method of the solubilization parameter of the invention comprises the following steps: (1) firstly, sealing the tip of a 5mL temperature-resistant glass pipette, and intercepting the required length for later use; (2) preparing a surfactant solution with a certain concentration, measuring a certain volume of aqueous solution by using a pipettor, adding the aqueous solution into a glass pipettor with a sealed tip, simultaneously recording the mass of the added solution by using an analytical balance, adding a certain amount of crude oil or simulated oil (the oil-water ratio is determined according to the experimental requirements) according to the same method, and recording the volume and the mass; recording the water phase and oil phase scales; (3) after the sample is added, sealing the upper opening of the glass pipette; (4) uniformly mixing by adopting vortex oscillation or rotation; (5) standing for a period of time at a set temperature, continuously shaking to gradually reach equilibrium, photographing to record the change of a phase state along with time, and calculating a solubilization parameter, wherein the formula is shown in (3):
wherein SP is a solubilization parameter, VS、VO、VWThe volume of surfactant, the volume of crude oil solubilized by the surfactant, and the volume of water solubilized by the surfactant, respectively.
The composite surfactant composition prepared by the invention is used in an amount of 0.01-0.15 wt% in percentage by mass, and can be used for the formation with the temperature of 50-120 ℃, the degree of mineralization of 5000-200000 Mg/L and Mg2++Ca 2+20 to 12000 mg/l, HCO3 -The dynamic interfacial tension value between the surfactant aqueous solution and the crude oil is measured to be 0-2000 mg/L of oilfield water and crude oil and can reach 10-2～10-4The mN/m low interfacial tension, the static adsorption capacity less than 2mg/g, 4 wt% of surfactant can well emulsify the crude oil, the maximum solubilization parameter is 23.7, and a better technical effect is achieved.
The composite oil displacement agent is used for simulated brine and crude oil with the formation temperature of 50-120 ℃ and the mineralization degree of 5000-200000 mg/L, and the composite oil displacement agent is formed by 0.01-0.15 wt% of surfactant composition, 0-0.3 wt% of polymer and 0-1.2 wt% of alkali according to mass percentageThe apparent viscosity of the oil displacement agent aqueous solution is measured, and the dynamic interfacial tension value between the oil displacement agent aqueous solution and the oil field dehydrated crude oil can reach 10-2～10-4mN/m. The evaluation in a physical simulation displacement laboratory shows that the oil displacement agent can improve the oil recovery rate of 26.38% to the maximum on the basis of water displacement, and a good technical effect is achieved.
Drawings
The zwitterionic compound and the surfactant containing polyether segments prepared by the invention can be applied to a Nicolet-5700 spectrometer and subjected to infrared spectroscopic analysis (the scanning range is 4000-400 cm)-1) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.
FIG. 1 is an infrared spectrum of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt. Wherein, 2918.4cm-1And 2850.4cm-1Is a characteristic peak of C-H stretching of methyl and methylene, 1629.9cm-1Is C ═ O stretching vibration absorption peak, 1546.8cm-1And 1602.8cm-1Is the stretching vibration peak of benzene ring, 1465.1cm-1Is a C-N bending vibration absorption peak, 1167.0cm-1And 1239.1cm-1Is a C-N stretching vibration peak of 700.0-800.0 cm-1Is the in-plane rocking absorption peak of CH plane in the benzene ring. FIG. 2 shows a mixed alcohol (C)14～18) Infrared spectrum of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether acetic acid. Wherein, 2922.0cm-1And 2853.0cm-1Is a characteristic peak of C-H stretching of methyl and methylene, 1757.2cm-1Is the C ═ O stretching vibration characteristic peak in carboxylic acid, 1457.2cm-1Out-of-plane bending vibration peak for OH, 1248.2cm-1Is C-O stretching vibration peak, 1098.1cm-1Characteristic absorption peaks of C-O-C ether bonds.
FIG. 3 is a graph of oil-water interfacial tension of 0.15% surfactant after aging for various periods of time.
Fig. 4 is a flow chart of an indoor core displacement experiment.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
(a) Preparation of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt
359.0 g (1 mol) of N-octadecyl-N-methylaniline, 174.8 g (1.5 mol) of sodium chloroacetate, and 750 g of a 50 wt% aqueous ethanol solution were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux for 8 hours to stop the reaction. Taking a small amount of reaction liquid for HPLC analysis, dissolving (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt and N-octadecyl-N-methylaniline according to the ratio of 96.7:3.3 with ethyl acetate for desalting for multiple times, removing organic solvent to obtain zwitterionic surfactant, and performing infrared spectroscopy analysis (scanning range is 4000-400 cm) by using a liquid film method by using an American Nicolet-5700 infrared spectrometer-1) The infrared spectrum is shown in figure 1. The remaining samples were left untreated and were ready for use.
(b) Preparation of composite surfactant composition S01
RO(CH2CH2O)2(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C)14～18) And 6.5 g of potassium hydroxide, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, slowly introducing 707.6 g (12.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum,cooling, neutralizing, and dehydrating to obtain mixed alcohol (C)14～18) 1080.8 g of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether, the yield was 96.5%.
(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring14～18) 560.0 g (0.5 mol) of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide are slowly dropped into 91.9 g (0.55 mol) of ethyl bromoacetate, the reaction temperature is controlled to 90 ℃ for reaction for 5 hours, 1200 g of water and 100 g of 95% ethanol are added after cooling, the mixture is continuously heated to reflux reaction for 3 hours, the mixture is cooled to 30 ℃, concentrated hydrochloric acid is added to adjust the pH value to be 3, a small amount of benzene is taken for extraction, an organic layer is separated after water washing, benzene is removed under reduced pressure to obtain a product, an American Nicolet-5700 infrared spectrometer is applied, and infrared spectrum analysis is carried out by adopting a liquid-film method (the scanning range is 4000-400 cm)-1) The infrared spectrum is shown in figure 2. . The remaining reaction solution was neutralized with 55.5 g (0.55 mol) of triethylamine, and an aqueous solution of ethanol containing 834.0 g (2.0 mol) of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium was added to obtain the desired composite surfactant composition S01.
[ example 2 ]
(a) Preparation of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium inner salt
359.0 g (1 mol) of N-dodecyl-N-hydroxyethyl aniline, 60.0 g (1.5 mol) of sodium hydroxide and 500 ml of benzene are mixed in a 5000 ml four-neck flask provided with a mechanical stirring device, a thermometer and a reflux condenser tube, the mixture is heated to 50 ℃, 174.8 g (1.5 mol) of sodium chloroacetate is added into a reaction bottle for four times, the mixture is heated to reflux reaction for 6 hours after the addition, the solvent benzene is evaporated under reduced pressure, 1500g of water is added into the mixture after the mixture is cooled to room temperature, the mixture is uniformly stirred, the mixture is heated to 75 ℃, 116.5 g (1.0 mol) of sodium chloroacetate is added into the reaction bottle for three times, the reaction is continued for 5 hours, and the reaction is stopped. A small amount of reaction liquid is taken for HPLC analysis, the ratio of (N-carboxymethyl-N-carboxymethyl oxyethyl-N-dodecyl) phenyl ammonium inner salt to N-dodecyl-N-hydroxyethyl aniline is 89.6:8.4, and the rest samples are not processed.
(b) Preparation of composite surfactant composition S02
(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to a reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 1015.7 g of dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether with a yield of 97.1%.
(2) Adding 52.3 g (0.05 mol) of the dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 8.0 g (0.2 mol) of sodium hydroxide into a 1000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 8.0 g (0.065 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reaction for 4 hours, cooling, adding 80 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 399.0 g (0.95 mole) of an aqueous solution of the inner salt of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S02.
[ example 3 ]
(a) Preparation of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt
274.0 g (1 mol) of N-dodecyl-N-methylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of 5 wt% aqueous isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 6 hours to stop the reaction. Taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt to N-dodecyl-N-methylaniline is 94.7:6.3, and the rest samples are not processed for later use.
(b) Preparation of anionic and Complex surfactant composition S03
(1) Adding 303 g (1 mol) of abietic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 145 ℃, slowly introducing 224.4 g (5.1 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, after the reaction is finished, cooling to 90 ℃, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 499.5 g of polyoxyethylene (5) ether ester abietic acid with the yield of 95.5%.
(2) Adding 261.5 g (0.5 mol) of rosin acid polyoxyethylene (5) ether ester synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 2000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dripping 135.8 g (0.75 mol) of n-propyl bromoacetate, controlling the reaction temperature to be 95 ℃ for reaction for 5 hours, cooling, adding 400 g of water and 75 g of 95% isopropanol, and continuously heating until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 249.1 grams (0.75 moles) of the inner salt of (N-carboxymethyl-N-dodecyl-N-methyl) phenylammonium was added and stirring continued at 45 deg.C for 3 hours to provide the desired composite surfactant composition S03.
[ example 4 ]
(a) Preparation of (N-carboxymethyl-N, N-dimethyl) -4-hexadecyl phenyl ammonium inner salt
345.0 g (1 mol) of N, N-dimethyl- (4-hexadecyl) aniline, 128.2 g (1.1 mol) of sodium chloroacetate and 600 g of a 15 wt% aqueous isopropanol solution were mixed in a 2000-ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 9 hours to stop the reaction. A small amount of the reaction solution was subjected to HPLC analysis, the ratio of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium inner salt to N, N-dimethyl- (4-hexadecyl) aniline was 91.2:8.8, and the remaining samples were left untreated and kept for future use.
(b) Preparation of composite surfactant composition S04
RO(CHCH3CH2O)12(CH2CH2O)2CH2COONa
Wherein R is iso-C13H27。
(1) Adding 200 g (1 mol) of isomeric tridecanol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 955.5 g of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether is obtained, and the yield is 97.1%.
(2) Adding 492 g (0.5 mol) of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dripping 79.6 g (0.65 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reaction for 4 hours, cooling, adding 700 g of water and 50 g of 95% ethanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 80.6 g (0.2 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S04.
[ example 5 ]
(a) Preparation of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenyl ammonium inner salt
345.0 g (1 mol) of N-hexadecyl-N-methyl-4-methylaniline, 357.3 g (1.8 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 800 g of a 25 wt% aqueous ethanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux reaction for 12 hours to stop the reaction. A small amount of the reaction solution was subjected to HPLC analysis, the ratio of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium inner salt to N-hexadecyl-N-methyl-4-methylaniline was 87.5:12.5, and the remaining sample was left untreated and was used for future use.
(b) Preparation of composite surfactant composition S05
(1) 276 g (1 mol) of dodecyl benzyl alcohol and 4.6 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the temperature is heated to 80-90 ℃, the dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, 469.8 g (8.1 mol) of propylene oxide is slowly introduced at 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, the temperature is adjusted to 140 ℃ after the reaction of the propylene oxide is finished, 44.0 g (1.0 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, 925.4 g of dodecyl benzyl alcohol polyoxyethylene (4), polyoxypropylene (8) and polyoxyethylene (1) ether are obtained, and the yield is 96.4%.
(2) And (b) adding 96.0 g (0.1 mol) of the dodecyl benzyl alcohol polyoxyethylene (4) polyoxypropylene (8) polyoxyethylene (1) ether synthesized in the step (b) (1) and 9.6 g (0.25 mol) of sodium hydroxide into a 5000-ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 21.7 g (0.12 mol) of isopropyl bromoacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 160 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 434.7 g (0.9 mole) of an aqueous solution of ethanol containing the inner salt of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium was added, and stirring was continued at 45 deg.C for 3 hours to obtain the desired composite surfactant composition S05.
[ example 6 ]
(a) Preparation of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt
121.0 g (1 mol) of N, N-dimethylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of a 5 wt% aqueous isopropanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of the (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt to the N, N-dimethylaniline is 95.1:4.9, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S06
(1) Adding 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, slowly introducing 350.9 g (6.05 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 88.0 g (2.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 894.9 g of isomeric hexadecanol polyoxyethylene (4), polyoxypropylene (6), polyoxyethylene (2) ether are obtained, and the yield is 94.2%.
(2) In a 2000 ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, 475.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether synthesized in the step (b) (1) and 87.0 g (1.5 mol) of potassium hydroxide are added under stirring, 102.4 g (0.75 mol) of isopropyl chloroacetate is slowly dropped, the reaction temperature is controlled at 100 ℃ for reaction for 3 hours, 600 g of water is added after cooling, and the mixture is continuously heated until reflux reaction for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 9.0 g (0.05 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium was added and stirring was continued at 40 deg.C for 5 hours to obtain the desired composite surfactant composition S06.
[ example 7 ]
(a) Preparation of (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt
144.0 g (1 mol) of N, N-diethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15 wt% aqueous solution of isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of the (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt to the N, N-diethylaniline is 92.5:7.5, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S07
RO(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C)14～18) Heating 6.5 g of potassium hydroxide to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 707.6 g (12.2 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C)14～18) 995.9 g of polyoxypropylene (12) polyoxyethylene (2) ether, 96.5% yield.
(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring14～18) 516.0 g (0.5 mol) of polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide were added dropwise slowly to 91.9 g (0.55 mol) of ethyl bromoacetate, the reaction temperature was controlled at 90 ℃ to react for 5 hours, 600 g of water and 100 g of 95% ethanol were added after cooling, the mixture was heated to reflux for 3 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust the pH to 3, 55.5 g (0.55 mol) of triethylamine was added to neutralize the produced carboxylic acid, and an aqueous isopropanol solution containing 24.8 g (0.12 mol) of (N-carboxymethyl-N, N-diethyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S07.
[ example 8 ]
(a) Preparation of (N-carboxymethyl-N-methyl-N-ethyl) phenylammonium inner salt
130.0 g (1 mol) of N-methyl-N-ethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15 wt% aqueous solution of isopropanol were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 6.5 hours, and the reaction was stopped. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-methyl-N-ethyl) phenyl ammonium inner salt to N-methyl-N-ethylaniline is 93.7:6.3, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S08
(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 121.8 g (2.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 312.4 g (7.1 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 665.8 g of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether in a yield of 97.2%.
(2) 342.5 g (0.5 mol) of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether synthesized in the step (b) (1) and 80.0 g (2.0 mol) of sodium hydroxide are added into a 5000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, 79.6 g (0.65 mol) of ethyl chloroacetate is slowly dropped into the reaction bottle, the reaction temperature is controlled to be 90 ℃ for reaction for 4 hours, 600 g of water and 100 g of 50% isopropanol are added after cooling, and the reaction bottle is continuously heated until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 56.4 grams (0.3 moles) of the inner (N-methyl-N-ethyl) phenylammonium salt was added and stirring continued at 40 deg.C for 4 hours to provide the desired composite surfactant composition S08.
[ example 9 ]
(a) The same as [ example 1 ] a.
(b) Preparation of composite surfactant composition S09
RO(CH2CH2O)2(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
Preparation of Mixed alcohol (C) in the same manner as in [ example 1 ]14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether.
Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether 560.0 g (0.5 mol), 56.0 g (1.0 mol) potassium hydroxide and 1000 ml benzene were reacted at 70 ℃ for 4 hours, then cooled to 87.4 g (0.75 mol) sodium chloroacetate was slowly added, refluxed for 8 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust pH to 3, benzene was evaporated under reduced pressure, 55.5 g (0.55 mol) triethylamine was added to neutralize the resulting carboxylic acid, and an aqueous ethanol solution containing 834.0 g (2.0 mol) (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S09.
[ example 10 ]
The same as [ example 1 ] except that 560.0 g (0.5 mol) of the alcohol (C) was mixed14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether without further reaction, 600 g of water, 73.0 g (1.0 mol) of N-butylamine were added, and 166.8 g (0.4 mol) of an aqueous ethanol solution of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium was added to obtain the desired complex surfactant composition S10.
[ example 11 ]
The same as in example 1, except that the alcohol solvent was distilled off under reduced pressure at the end of the reaction in the steps (a) and (b), to obtain the desired surfactant composition S11.
[ example 12 ]
The same as [ example 1 ] except that the mixed alcohol (C) was replaced with 0.5 mol of coconut oil acid triethylamine salt14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) Ether acetic acid triethylamine salt, and 834.0 g (2.0 moles) of an aqueous ethanol solution of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium were added to obtain the desired complex surfactant composition S12.
[ example 13 ]
The same as [ example 1 ] except that the mixed alcohol (C) was replaced with 0.5 mol of triethylamine dodecylsulfonate14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) Ether acetic acid triethylamine salt, and an aqueous ethanol solution containing 417.0 g (1.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S13.
[ example 14 ]
(a) The same as [ example 6 ] a.
(b) Preparation of composite surfactant composition S14
(1) Adding 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 397.9 g of isomeric hexadecanol polyoxyethylene (4) ether is obtained, and the yield is 95.2%.
(2) Adding 4209.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) ether synthesized in the step (b) (1), 87.0 g (1.5 mol) of potassium hydroxide and 500 ml of toluene into a 2000 ml reaction bottle provided with a mechanical stirring, thermometer and reflux condenser pipe, stirring, raising the temperature to 75 ℃ for reacting for 4 hours, cooling to 60 ℃, slowly adding 299.2 g (1.5 mol) of 3-chloro-2-hydroxy sodium propanesulfonate, controlling the reaction temperature to 90 ℃ for reacting for 8 hours, cooling, adding 600 g of water, adding an isopropanol aqueous solution containing 36.0 g (0.2 mol) of an isopropanol aqueous solution of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt, and continuously stirring at 40 ℃ for 5 hours to obtain the required composite surfactant composition S14.
[ example 15 ]
And (3) performance experiments of the composite surfactant composition as an oil displacement agent.
Simulated water with different salt contents is prepared, and the composition is shown in table 1. Crude oil was used for the experiments in the oil field, the properties of which are shown in table 2, after dehydration.
The phase state experiment can well reflect the solubilizing capability of the surfactant to the crude oil, and the solubilizing parameters of the surfactant to the crude oil and the optimal salt content of the surfactant are obtained. The experimental process is as follows: first, 4.0 wt.% aqueous solutions of different salt contents (1) were prepared#～9#Simulated water), adding 2.5mL of the solution into a 5mL pipette with one end sealed, adding 2.5mL of dehydrated crude oil (the volume ratio of oil to water is 1:1), sealing the upper end, recording the initial volume of oil and water, fully mixing, placing the mixture into a stainless steel sealed container, placing the container in an oven, standing at constant temperature until the volume of each phase is not changed, recording the volume of each phase, calculating the solubilization parameter of the surfactant to the crude oil, and taking the salinity when the solubilization parameter is maximum as the optimal salt content, wherein the result is shown in Table 2.
The static adsorption test is mainly based on the research of adsorption loss amount of the surfactant on the formation rock core, and the economy and the formability of the surfactant synthesized in the embodiment in the field application of improving the crude oil recovery rate are explored. The experimental process is as follows: mixing 3g of simulated saline solution of the surfactant and 1g of clay-containing quartz sand, oscillating for 24h at a set temperature, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant by using High Performance Liquid Chromatography (HPLC), and calculating the adsorption amount of the surfactant in mg/g, wherein the result is shown in Table 3. Wherein, the clay-containing quartz sand comprises the following components: 10 wt% of kaolin and 90 wt% of 100-200 mesh quartz sand.
The composite surfactant composition was dissolved in the corresponding simulated water, and the oil-water interfacial tension of the surfactant solution on crude oil was measured, and the results are shown in table 4. Combining 0.15 wt% of composite surfactantFilling the substance analog saline solution into 20 ml ampoule, sealing and placing into oven, measuring oil-water interfacial tension after different ageing time, finding that the oil-water interfacial tension can still be maintained at 10-3～10-4Ultra low values of mN/m are shown in FIG. 3. The oil-water interfacial tension (IFT) was measured by a model TX500 rotary droplet interfacial tensiometer manufactured by Texas university, USA and a SVT 20 high temperature rotary droplet interfacial tensiometer manufactured by Dataphysics.
[ COMPARATIVE EXAMPLE 1 ]
Octadecyl benzyl methyl betaine
Octadecyl dimethyl betaine
The same as in example 1 except that (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was replaced with commercially available octadecyl benzyl methyl betaine or octadecyl dimethyl betaine, the rest was the same, to give surfactant compositions S15 and S16. The performance test was carried out as in example 15, and the results are shown in Table 5.
[ COMPARATIVE EXAMPLE 2 ]
RO(CH2CH2O)4(CHCH3CH2O)12CH2COOH.N(C2H5)3
The same as in example 1 except that in step (b) (1), 180.4 g (4.1 mol) of ethylene oxide was introduced followed by 707.6 g (12.2 mol) of propylene oxide to give the isomeric tridecanol polyoxyethylene (4) polyoxypropylene (12) ether, and the same applies to give surfactant composition S17. The performance test was carried out as in example 15, and the results are shown in Table 5.
[ COMPARATIVE EXAMPLE 3 ]
The difference is that the propylene oxide and the ethylene oxide are not reacted step by step sequentially, but are reacted in one step after mixing, namely a mixture of 707.6 g (12.2 mol) of propylene oxide and 180.4 g (4.1 mol) of ethylene oxide is slowly introduced at 110-150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, and the rest is the same, so that S18 is obtained, and the performance experiment is carried out in the same way as in example 15, and the result is shown in Table 5.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
[ example 16 ]
(a) Preparation of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt
359.0 g (1 mol) of N-octadecyl-N-methylaniline are mixed with 174.8 g (1.5 mol) of sodium chloroacetate, 750 g of 50 wt.% aqueous ethanol solution in 2000 ml of a mixture provided with mechanical stirring, thermometer and reflux condenserThe reaction was stopped by heating the mixture in a four-necked flask to reflux for 8 hours. Taking a small amount of reaction liquid for HPLC analysis, dissolving (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt and N-octadecyl-N-methylaniline according to the ratio of 96.7:3.3 with ethyl acetate for desalting for multiple times, removing organic solvent to obtain zwitterionic surfactant, and performing infrared spectroscopy analysis (scanning range is 4000-400 cm) by using a liquid film method by using an American Nicolet-5700 infrared spectrometer-1) The infrared spectrum is shown in figure 1. The remaining samples were left untreated and were ready for use.
(b) Preparation of composite surfactant composition S01
RO(CH2CH2O)2(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C)14～18) And 6.5 g of potassium hydroxide, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, slowly introducing 707.6 g (12.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C)14～18) 1080.8 g of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether, the yield was 96.5%.
(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring14～18) 560.0 g (0.5 mol) of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide were added dropwise to 91.9 g (0.55 mol) of ethyl bromoacetate slowly, and the reaction temperature was controlledReacting at 90 ℃ for 5 hours, cooling, adding 1200 g of water and 100 g of 95% ethanol, continuously heating until reflux reaction is carried out for 3 hours, cooling to 30 ℃, adding concentrated hydrochloric acid to adjust the pH to 3, taking a small amount of benzene for extraction, washing with water, separating an organic layer, removing benzene under reduced pressure to obtain a product, applying a Nicolet-5700 infrared spectrometer, and carrying out infrared spectrum analysis (the scanning range is 4000-400 cm)-1) The infrared spectrum is shown in figure 2. . The remaining reaction solution was neutralized with 55.5 g (0.55 mol) of triethylamine, and an aqueous solution of ethanol containing 834.0 g (2.0 mol) of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium was added to obtain the desired composite surfactant composition S01.
Simulated water with different salt contents is prepared, and the composition is shown in table 1. Crude oil was used for the experiments in the oil field, the properties of which are shown in table 2, after dehydration.
The phase state experiment can well reflect the solubilizing capability of the surfactant to the crude oil, and the solubilizing parameters of the surfactant to the crude oil and the optimal salt content of the surfactant are obtained. The experimental process is as follows: first, 4.0 wt% aqueous surfactant solutions (1) of different salt contents were prepared#～9#Simulated water), adding 2.5mL of the solution into a 5mL pipette with one end sealed, adding 2.5mL of dehydrated crude oil (the volume ratio of oil to water is 1:1), sealing the upper end, recording the initial volume of oil and water, fully mixing, placing the mixture into a stainless steel sealed container, placing the container in an oven, standing at constant temperature until the volume of each phase is not changed, recording the volume of each phase, calculating the solubilization parameter of the surfactant to the crude oil, and taking the salinity when the solubilization parameter is maximum as the optimal salt content, wherein the result is shown in Table 2.
Mixing 3g of surfactant simulated aqueous solution and 1g of clay-containing quartz sand, oscillating for 24h, cooling, centrifuging, taking supernatant to measure the adsorption capacity in mg/g, and obtaining the result shown in Table 3. Wherein, the adsorption capacity is determined by a TOC method, and the clay-containing quartz sand comprises the following components: 10 wt% of kaolin and 90 wt% of 100-200 mesh quartz sand.
(c) Performance test of oil-displacing agent
(1) Preparation of oil-displacing agent aqueous solution
Preparing an S01 surfactant composition, a modified polyacrylamide polymer (P1, the molar ratio of the copolymer AM/AMPS is 1/0.05, and the viscosity average molecular weight is 2500 ten thousand) and an aqueous solution of diethanol amine by using simulated water, and mixing and diluting the aqueous solution according to a required proportion to obtain the uniform oil displacement agent.
(2) The viscosity and the oil-water interfacial tension of the oil-displacing agent were measured and compared with those of S01 and P1, as shown in Table 6. The apparent viscosity was measured by a model HAAKE MARS III rotational rheometer, and the interfacial tension was measured by a model TX500 rotational droplet interfacial tension meter manufactured by texas university, usa and a SVT 20 high temperature rotational droplet interfacial tension meter of Dataphysics corporation.
(3) And drying the artificial core at constant temperature to constant weight, measuring the average diameter and the length of the core, weighing the dry weight of the core, and measuring the gas logging permeability of the core. The pore volume was tested with the above simulated brine saturated core. And (4) recording the volume of the saturated crude oil by using the oil field dehydrated crude oil saturated core. At the temperature of 75 ℃, 11# simulation water is used for driving until the water content of produced liquid reaches 100%, the recovery ratio of the crude oil improved by water driving is calculated, after 0.3PV (core pore volume) oil displacement agent is injected, the water is driven until the water content reaches 100%, the percentage of the crude oil improved on the basis of water driving is calculated, and meanwhile, the comparison with the injection of the same PV surfactant and polymer is shown in the table 6. The flow of the simulated core displacement test used is shown in fig. 4. The viscosity of the dehydrated crude oil is 2.5 mPa.s.
[ example 17 ]
(a) Preparation of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium inner salt
359.0 g (1 mol) of N-dodecyl-N-hydroxyethyl aniline, 60.0 g (1.5 mol) of sodium hydroxide and 500 ml of benzene are mixed in a 5000 ml four-neck flask provided with a mechanical stirring device, a thermometer and a reflux condenser tube, the mixture is heated to 50 ℃, 174.8 g (1.5 mol) of sodium chloroacetate is added into a reaction bottle for four times, the mixture is heated to reflux reaction for 6 hours after the addition, the solvent benzene is evaporated under reduced pressure, 1500g of water is added into the mixture after the mixture is cooled to room temperature, the mixture is uniformly stirred, the mixture is heated to 75 ℃, 116.5 g (1.0 mol) of sodium chloroacetate is added into the reaction bottle for three times, the reaction is continued for 5 hours, and the reaction is stopped. A small amount of reaction liquid is taken for HPLC analysis, the ratio of (N-carboxymethyl-N-carboxymethyl oxyethyl-N-dodecyl) phenyl ammonium inner salt to N-dodecyl-N-hydroxyethyl aniline is 89.6:8.4, and the rest samples are not processed.
(b) Preparation of composite surfactant composition S02
(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to a reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 16 to obtain 1015.7 g of dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether with a yield of 97.1%.
(2) Adding 52.3 g (0.05 mol) of the dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 8.0 g (0.2 mol) of sodium hydroxide into a 1000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 8.0 g (0.065 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reaction for 4 hours, cooling, adding 80 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 399.0 g (0.95 mole) of an aqueous solution of the inner salt of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S02. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 16 ] except that S02 was used instead of S01, a hydrophobically associating polymer P2 (m/AM/AMPS/2-acrylamidododecylsulfonic acid molar ratio 1/0.45/0.002, viscosity average molecular weight 1750 ten thousand) was used instead of the modified polyacrylamide polymer (P1, m/AMPS molar ratio 1/0.05, viscosity average molecular weight 2500 ten thousand), diethanolamine was used instead of sodium carbonate, and 9# simulated water were used to prepare an oil displacement agent aqueous solution at a temperature of 110 ℃ and a crude oil viscosity of 1.9mpa.s, and the results are shown in table 7.
[ example 18 ]
(a) Preparation of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt
274.0 g (1 mol) of N-dodecyl-N-methylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of 5 wt% aqueous isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 6 hours to stop the reaction. Taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt to N-dodecyl-N-methylaniline is 94.7:6.3, and the rest samples are not processed for later use.
(b) Preparation of anionic and Complex surfactant composition S03
(1) Adding 303 g (1 mol) of abietic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 145 ℃, slowly introducing 224.4 g (5.1 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, after the reaction is finished, cooling to 90 ℃, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 499.5 g of polyoxyethylene (5) ether ester abietic acid with the yield of 95.5%.
(2) Adding 261.5 g (0.5 mol) of rosin acid polyoxyethylene (5) ether ester synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 2000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dripping 135.8 g (0.75 mol) of n-propyl bromoacetate, controlling the reaction temperature to be 95 ℃ for reaction for 5 hours, cooling, adding 400 g of water and 75 g of 95% isopropanol, and continuously heating until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 249.1 grams (0.75 moles) of the inner salt of (N-carboxymethyl-N-dodecyl-N-methyl) phenylammonium was added and stirring continued at 45 deg.C for 3 hours to provide the desired composite surfactant composition S03.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 16 ] except that S03 was used instead of S01, a hydrophobically associating polymer (P3, molar ratio of co-AM/AMPS/2-acrylamidododecylsulfonic acid 1/0.35/0.0015, viscosity average molecular weight 2055 ten thousand) was used instead of the modified polyacrylamide polymer (P1, molar ratio of co-AM/AMPS 1/0.05, viscosity average molecular weight 2500 ten thousand), diethanolamine was used instead of sodium carbonate, 12# simulated water was used to prepare an oil displacement agent aqueous solution at 90 ℃ and crude oil viscosity 2.1mpa.s, and the results are shown in table 7.
[ example 19 ]
(a) Preparation of (N-carboxymethyl-N, N-dimethyl) -4-hexadecyl phenyl ammonium inner salt
345.0 g (1 mol) of N, N-dimethyl- (4-hexadecyl) aniline, 128.2 g (1.1 mol) of sodium chloroacetate and 600 g of a 15 wt% aqueous isopropanol solution were mixed in a 2000-ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 9 hours to stop the reaction. A small amount of the reaction solution was subjected to HPLC analysis, the ratio of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium inner salt to N, N-dimethyl- (4-hexadecyl) aniline was 91.2:8.8, and the remaining samples were left untreated and kept for future use.
(b) Preparation of composite surfactant composition S04
RO(CHCH3CH2O)12(CH2CH2O)2CH2COONa
Wherein R is iso-C13H27。
(1) Adding 200 g (1 mol) of isomeric tridecanol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 955.5 g of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether is obtained, and the yield is 97.1%.
(2) Adding 492 g (0.5 mol) of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dripping 79.6 g (0.65 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reaction for 4 hours, cooling, adding 700 g of water and 50 g of 95% ethanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 80.6 g (0.2 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S04. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 18 ] except that S04 was used in place of S03 and 10# simulated water to prepare an aqueous solution of an oil-displacing agent at a temperature of 85 ℃ and a viscosity of dehydrated crude oil of 33.5mPa.s, the results are shown in Table 7.
[ example 20 ]
(a) Preparation of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenyl ammonium inner salt
345.0 g (1 mol) of N-hexadecyl-N-methyl-4-methylaniline, 357.3 g (1.8 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 800 g of a 25 wt% aqueous ethanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux reaction for 12 hours to stop the reaction. A small amount of the reaction solution was subjected to HPLC analysis, the ratio of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium inner salt to N-hexadecyl-N-methyl-4-methylaniline was 87.5:12.5, and the remaining sample was left untreated and was used for future use.
(b) Preparation of composite surfactant composition S05
(1) 276 g (1 mol) of dodecyl benzyl alcohol and 4.6 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the temperature is heated to 80-90 ℃, the dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, 469.8 g (8.1 mol) of propylene oxide is slowly introduced at 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, the temperature is adjusted to 140 ℃ after the reaction of the propylene oxide is finished, 44.0 g (1.0 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, 925.4 g of dodecyl benzyl alcohol polyoxyethylene (4), polyoxypropylene (8) and polyoxyethylene (1) ether are obtained, and the yield is 96.4%.
(2) And (b) adding 96.0 g (0.1 mol) of the dodecyl benzyl alcohol polyoxyethylene (4) polyoxypropylene (8) polyoxyethylene (1) ether synthesized in the step (b) (1) and 9.6 g (0.25 mol) of sodium hydroxide into a 5000-ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 21.7 g (0.12 mol) of isopropyl bromoacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 160 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 434.7 g (0.9 mole) of an aqueous solution of ethanol containing the inner salt of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium was added, and stirring was continued at 45 deg.C for 3 hours to obtain the desired composite surfactant composition S05. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 16 ] except that S05 was used instead of S01, and high molecular weight anionic polyacrylamide P4 (viscosity average molecular weight 2300 ten thousand) was used instead of the modified polyacrylamide polymer (P1, copolymerization AM/AMPS molar ratio 1/0.05, viscosity average molecular weight 2500 ten thousand), and 11# simulated water was used to prepare an oil displacement agent aqueous solution at 55 ℃ and crude oil viscosity 125.9mpa.s, the results of which are shown in table 6.
[ example 21 ]
(a) Preparation of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt
121.0 g (1 mol) of N, N-dimethylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of a 5 wt% aqueous isopropanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of the (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt to the N, N-dimethylaniline is 95.1:4.9, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S06
(1) Adding 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, slowly introducing 350.9 g (6.05 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 88.0 g (2.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 894.9 g of isomeric hexadecanol polyoxyethylene (4), polyoxypropylene (6), polyoxyethylene (2) ether are obtained, and the yield is 94.2%.
(2) In a 2000 ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, 475.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether synthesized in the step (b) (1) and 87.0 g (1.5 mol) of potassium hydroxide are added under stirring, 102.4 g (0.75 mol) of isopropyl chloroacetate is slowly dropped, the reaction temperature is controlled at 100 ℃ for reaction for 3 hours, 600 g of water is added after cooling, and the mixture is continuously heated until reflux reaction for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 9.0 g (0.05 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium was added and stirring was continued at 40 deg.C for 5 hours to obtain the desired composite surfactant composition S06. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 19 ] except that an aqueous displacement agent solution was prepared by replacing S04 with S06, and the results are shown in table 7.
[ example 22 ]
(a) Preparation of (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt
144.0 g (1 mol) of N, N-diethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15 wt% aqueous solution of isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of the (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt to the N, N-diethylaniline is 92.5:7.5, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S07
RO(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C)14～18) Heating 6.5 g of potassium hydroxide to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 707.6 g (12.2 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C)14～18) 995.9 g of polyoxypropylene (12) polyoxyethylene (2) ether, 96.5% yield.
(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring14～18) 516.0 g (0.5 mol) of polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide were added dropwise slowly to 91.9 g (0.55 mol) of ethyl bromoacetate, the reaction temperature was controlled at 90 ℃ to react for 5 hours, 600 g of water and 100 g of 95% ethanol were added after cooling, the mixture was heated to reflux for 3 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust the pH to 3, 55.5 g (0.55 mol) of triethylamine was added to neutralize the produced carboxylic acid, and an aqueous isopropanol solution containing 24.8 g (0.12 mol) of (N-carboxymethyl-N, N-diethyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S07.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3, and the aqueous displacement agent solution was prepared by substituting S07 for S01 and the results are shown in table 6.
[ example 23 ]
(a) Preparation of (N-carboxymethyl-N-methyl-N-ethyl) phenylammonium inner salt
130.0 g (1 mol) of N-methyl-N-ethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15 wt% aqueous solution of isopropanol were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 6.5 hours, and the reaction was stopped. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-methyl-N-ethyl) phenyl ammonium inner salt to N-methyl-N-ethylaniline is 93.7:6.3, and the rest samples are not processed for later use.
(b) Preparation of composite surfactant composition S08
(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 121.8 g (2.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 312.4 g (7.1 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60 MPa. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 16 to obtain 665.8 g of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether, and the yield thereof was 97.2%.
(2) 342.5 g (0.5 mol) of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether synthesized in the step (b) (1) and 80.0 g (2.0 mol) of sodium hydroxide are added into a 5000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, 79.6 g (0.65 mol) of ethyl chloroacetate is slowly dropped into the reaction bottle, the reaction temperature is controlled to be 90 ℃ for reaction for 4 hours, 600 g of water and 100 g of 50% isopropanol are added after cooling, and the reaction bottle is continuously heated until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 56.4 grams (0.3 moles) of an aqueous isopropanol solution of the inner (N-methyl-N-ethyl) phenylammonium salt was added and stirring continued at 40 deg.C for 4 hours to provide the desired composite surfactant composition S08. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
(c) Performance test of oil-displacing agent
The same as [ example 18 ] except that an aqueous displacement agent solution was prepared by replacing S03 with S08, and the results are shown in table 7.
[ example 24 ]
(a) The same as [ example 16 ] a.
(b) Preparation of composite surfactant composition S09
RO(CH2CH2O)2(CHCH3CH2O)12(CH2CH2O)2CH2COOH.N(C2H5)3
Wherein, the carbon chain distribution of R is as follows: c14＝5.53％、C16＝62.93％、C18＝31.54％。
In the same manner as [ example 16 ] preparation of Mixed alcohol (C)14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether.
The mixed alcohol (C) added with stirring in a 5000 ml reaction flask equipped with mechanical stirring, thermometer and reflux condenser14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether 560.0 g (0.5 mol), 56.0 g (1.0 mol) potassium hydroxide and 1000 ml benzene were reacted at 70 ℃ for 4 hours, then the temperature was reduced to 87.4 g (0.75 mol) sodium chloroacetate was slowly added, the mixture was refluxed for 8 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust the pH to 3, benzene was evaporated under reduced pressure, 55.5 g (0.55 mol) triethylamine was added to neutralize the generated carboxylic acid, and an aqueous ethanol solution containing 834.0 g (2.0 mol) (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain an aqueous solution of ethanolThe desired complex surfactant composition S09.
Similarly [ example 16 ], phase and static adsorption experiments were performed, the results are shown in tables 2 and 3, and the oil displacement experiment was performed by preparing an oil displacement agent aqueous solution using S09 instead of S01, and the results are shown in table 6.
[ example 25 ]
The same as [ example 16 ] except that 560.0 g (0.5 mol) of the alcohol (C) was mixed14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether without further reaction, 600 g of water, 73.0 g (1.0 mol) of N-butylamine were added, and 166.8 g (0.4 mol) of an aqueous ethanol solution of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium was added to obtain the desired complex surfactant composition S10.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S10 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and oil displacement experiments are carried out, and the results are shown in Table 6.
[ example 26 ]
The same as in example 16, except that the alcohol solvent was distilled off under reduced pressure at the end of the reaction in the steps (a) and (b), to obtain the desired surfactant composition S11.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S11 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and oil displacement experiments are carried out, and the results are shown in Table 6.
[ example 27 ]
The same as [ example 16 ] except that the mixed alcohol (C) was replaced with 0.5 mol of coconut oil acid triethylamine salt14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) Ether acetic acid triethylamine salt, and 834.0 g (2.0 moles) of an aqueous ethanol solution of the inner salt of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium were added to obtain the desired complex surfactant composition S12.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S12 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and oil displacement experiments are carried out, and the results are shown in Table 6.
[ example 28 ]
The same as [ example 16 ] except that the mixed alcohol (C) was replaced with 0.5 mol of triethylamine dodecylsulfonate14～18) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) Ether acetic acid triethylamine salt, and an aqueous ethanol solution containing 417.0 g (1.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S13.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S13 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and oil displacement experiments are carried out, and the results are shown in Table 6.
[ example 29 ]
(a) The same as [ example 21 ] a.
(b) Preparation of composite surfactant composition S14
(1) Adding 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 397.9 g of isomeric hexadecanol polyoxyethylene (4) ether is obtained, and the yield is 95.2%.
(2) Adding 4209.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) ether synthesized in the step (b) (1), 87.0 g (1.5 mol) of potassium hydroxide and 500 ml of toluene into a 2000 ml reaction bottle provided with a mechanical stirring, thermometer and reflux condenser pipe, stirring, raising the temperature to 75 ℃ for reacting for 4 hours, cooling to 60 ℃, slowly adding 299.2 g (1.5 mol) of 3-chloro-2-hydroxy sodium propanesulfonate, controlling the reaction temperature to 90 ℃ for reacting for 8 hours, cooling, adding 600 g of water, adding an isopropanol aqueous solution containing 36.0 g (0.2 mol) of an isopropanol aqueous solution of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt, and continuously stirring at 40 ℃ for 5 hours to obtain the required composite surfactant composition S14.
Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.
Similarly, (example 19) S14 was used instead of S04, and ethanolamine was used instead of diethanolamine to prepare an oil displacement agent aqueous solution, and oil displacement experiments were performed, and the results are shown in table 7.
[ COMPARATIVE EXAMPLE 4 ]
Octadecyl benzyl methyl betaine
Octadecyl dimethyl betaine
The same as in example 16 except that (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was replaced with commercially available octadecyl benzyl methyl betaine or octadecyl dimethyl betaine, the rest was the same, to give surfactant compositions S15 and S16. The phase experiment and the static adsorption experiment were carried out as in example 16, and the results are shown in Table 5. The results of preparing the oil-displacing agent aqueous solution by replacing S01 with S15 and S16 are shown in Table 8.
[ COMPARATIVE EXAMPLE 5 ]
RO(CH2CH2O)4(CHCH3CH2O)12CH2COOH.N(C2H5)3
The same as in example 16 except that in step (b) (1), 180.4 g (4.1 mol) of ethylene oxide was introduced followed by 707.6 g (12.2 mol) of propylene oxide to give the isomeric tridecanol polyoxyethylene (4) polyoxypropylene (12) ether, the same applies to give surfactant composition S17.
The phase experiment and the static adsorption experiment were carried out as in example 16, and the results are shown in Table 5. The results of preparing the oil-displacing agent aqueous solution with S17 instead of S01 are shown in table 8.
[ COMPARATIVE EXAMPLE 6 ]
The same as example 16, except that the reaction with propylene oxide and ethylene oxide was not carried out successively in steps, but was carried out in one step after mixing, i.e., a mixture of 707.6 g (12.2 mol) of propylene oxide and 180.4 g (4.1 mol) of ethylene oxide was slowly introduced at 110 to 150 ℃ under a controlled pressure of 0.60MPa or less, and the rest was the same, thereby obtaining S18.
The phase experiment and the static adsorption experiment were carried out as in example 16, and the results are shown in Table 5. The results of preparing the oil-displacing agent aqueous solution with S18 instead of S01 are shown in table 8.
[ COMPARATIVE EXAMPLE 7 ]
The same as [ example 16 ] except that the hydrophobically associative polymer P1 was replaced with a high molecular weight anionic polyacrylamide P4 (having a viscosity average molecular weight of 2300 ten thousand), and the results were as shown in FIG. 8.
TABLE 6
TABLE 7
TABLE 8
Claims (10)
1. A composite surfactant composition comprising the following components:
(1) a zwitterionic compound;
(2) a surfactant containing polyether segments or no polyether segments;
wherein the molar ratio of the zwitterionic compound to the surfactant containing polyether or no polyether segment is (1:0.02) - (1: 20); the molecular general formula of the zwitterionic compound is shown as the formula (I):
in the formula (I), R1And R4Is hydrogen, C2～C32Alkyl or substituted alkyl of (CH R')cOH、(CH R')dCH3One of phenyl, substituted phenyl or benzyl, R2Y-Is C1～C5Alkylene or substituted alkylene carboxylates, C1～C5Alkyl or substituted alkyl sulfonates, C1～C5Hydrocarbyl or substituted hydrocarbyl phosphate or C1～C5At least one of hydrocarbyl or substituted hydrocarbyl sulfate, R3Is hydrogen, C2～C32Alkyl or substituted alkyl (CHR')eOH, halogen, amino, carboxylic acid group or sulfonic group, R 'and R' are independently selected from H, CH3Or C2H5C is any integer from 1 to 4, d is any integer from 0 to 5, and e is any integer from 0 to 4;
the molecular general formula of the surfactant containing polyether segments or not containing polyether segments is as follows:
in the formula (II), R5Is C8～C30Or one of the aliphatic or substituted aliphatic radicals of (A), or from C4～C20A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R5O is abietate; m1 and m2 are the addition number of ethoxy groups, m1 is 0-50, and m2 is 0-50; n is the addition number of the propoxy groups, and n is 0-100; k is 0 or 1; when k is 1, X is hydrogen or R5Z，R5Is C1～C5Z is COOM, SO3N or hydrogen, M, N is selected from hydrogen ion, cation or cation group; when k is 0, X isCOOM、SO3And one of N, M, N is selected from hydrogen ion, cation or cation group.
2. The composite surfactant composition according to claim 1, wherein said M, N is selected from the group consisting of hydrogen ion, alkali metal cation, and a complex of formula NR7(R8)(R9)(R10) At least one of the groups shown, wherein R7、R8、R9、R10Is independently selected from H, (CHR)0)fOH or (CHR)0)gCH3One of (1), R0Is H, CH3Or C2H5Wherein f is any integer from 1 to 4, and g is any integer from 0 to 5.
3. The composite surfactant composition according to claim 1 or 2, characterized in that R is1And R4Is hydrogen, C8～C24One of alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl; r2Y-Is C1～C3Alkylene or substituted alkylene carboxylates, C1～C3One of alkyl or substituted alkyl sulfonate, R3Is hydrogen, C8～C24One of alkyl or substituted alkyl, methyl, ethyl, phenyl, hydroxyl, amino, carboxylic acid group or sulfonic acid group; r ', R', R0Independently selected from H or CH3(ii) a c is 1-2, d is 0-1, e is 0-1, f is 1-2, g is 0-1, and j is 0 or 1; the R is5Is C12～C24Or a substituted aliphatic radical of4～C20Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)6H5C(CH3)2) A substituted benzene or naphthalene ring; r6Is C1～C3An alkylene group of (a); m1 is 0-10, m2 is 0-10, and n is 0-20.
4. The composite surfactant composition according to claim 1, characterized in that the composite surfactant composition further comprises:
(3) a small molecule alcohol;
(4) a small molecule amine;
(5) salt;
(6) an inorganic base;
wherein the molar ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the inorganic base is 1 (0.02-20): 0-10; the small molecular alcohol is selected from C1～C8The fatty alcohol of (a); the small molecule amine is selected from C1～C8At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is further preferably selected from at least one of alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates: the mole ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the small molecular alcohol, the small molecular amine, the salt and the alkali is preferably 1 to (0.05-20): (0-15): (0-5).
5. A process for preparing a composite surfactant composition as claimed in any one of claims 1 to 4, comprising the steps of:
(a) preparation of zwitterionic compound:
will be provided with
With ionizing agents R2Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain a water solution or an alcohol water solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C1～C5The fatty alcohol of (a);
(b) preparation of the composite surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;
wherein the surfactant with the structure shown in the formula (II) is prepared by adopting the following method optionally:
in the presence of an alkaline catalyst, R5OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); or further reacting through an optional step (II) to obtain the ionic polyether compound with the structure shown in the formula (II):
② the polyether compound obtained in the step I and an ionizing agent Y0R6Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, and the mixture is stirred and reacted for 3-15 hours at the reaction temperature of 50-120 ℃ to obtain the ionic polyether compound; wherein, Y0Selected from chlorine, bromine or iodine;
or: ② the polyether compound obtained in the step I and an ionizing agent Y0R6Z0And alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, the mixture is stirred and reacted for 3-15 hours at the reaction temperature of 50-120 ℃, water is continuously added for saponification reaction, and the ionic polyether compound is obtained after refluxing for 1-10 hours; wherein, Y0Selected from chlorine, bromine or iodine, Z0Is selected from COOR0,R0Is selected from C1～C8Alkyl group of (1).
6. The process for preparing a composite surfactant composition according to claim 5, wherein said ionizing agent R is2Y is at least one of alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, alkali metal salt of 2-chloroethanesulfonic acid, alkali metal salt of 1, 3-propanesultone, chloroacetic acid and alkali metal salt of chloroacetic acid sulfonating agent, and the alcohol is selected from C1～C4The fatty alcohol of (a); the above-mentioned
And R2Y is in a molar ratio of 1:1 to3; the reaction temperature in the first step is 120-160 ℃, the pressure is 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; in the second step, the alkali metal hydroxide is at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is 1 (0.3-3) to (0.2-6), and Y is0Is one of chlorine or bromine, R0Is C1～C4Alkyl group of (1).
7. Use of the composite surfactant composition according to any one of claims 1 to 6 in oil fields.
8. The composite oil displacement agent comprises the following components in parts by weight:
(1)1 part of the composite surfactant composition as claimed in any one of claims 1 to 4 or the surfactant composition prepared by the preparation method as claimed in any one of claims 5 to 6;
(2)0 to 20 parts of a polymer and more than 0 part of a polymer;
(3) 0-30 parts of alkali; wherein the polymer is preferably at least one of anionic polyacrylamide, temperature-resistant and salt-resistant modified polyacrylamide, hydrophobically associating polyacrylamide or polymer microspheres; further preferably, the temperature-resistant and salt-resistant modified polyacrylamide molecular chain preferably comprises an acrylamide structural unit and a 2-acrylamido-2-methylpropanesulfonic acid structural unit, wherein the molar ratio of the acrylamide structural unit to the 2-acrylamido-2-methylpropanesulfonic acid structural unit is preferably (0.1-40) to 1, and the viscosity-average molecular weight is preferably 800-2500 ten thousand; the molecular chain of the hydrophobic association polymer preferably comprises an acrylamide structural unit, a temperature-resistant and salt-resistant monomer structural unit and a hydrophobic monomer structural unit, wherein the molar ratio of the acrylamide structural unit to the temperature-resistant and salt-resistant monomer structural unit to the hydrophobic monomer structural unit is preferably 1: (0.1-40): (0.001 to 0.05) and preferably has a viscosity average molecular weight of 500 to 2500 ten thousand; in the oil displacement agent, the mass ratio of the surfactant composition to the polymer to the alkali is preferably 1 to (0.1-2): (0-5).
9. The method for preparing the composite oil-displacing agent according to claim 8, comprising the steps of:
(a) preparation of zwitterionic compound:
will be provided with
With ionizing agents R2Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain a water solution or an alcohol water solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C1～C5The fatty alcohol of (a);
(b) preparation of surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;
wherein the surfactant with the structure shown in the formula (II) is prepared by adopting the following method optionally:
in the presence of an alkaline catalyst, R5OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); or further reacting through an optional step (II) to obtain the ionic polyether compound with the structure shown in the formula (II):
② the polyether compound obtained in the step I and an ionizing agent Y0R6Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, and the mixture is stirred and reacted for 3-15 hours at the reaction temperature of 50-120 ℃ to obtain the ionic polyether compound; wherein, Y0Selected from chlorine, bromine or iodine;
or: ② the polyether compound obtained in the step I and an ionizing agent Y0R6Z0And alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1 (0.1-20) to 0.1-20, and stirringReacting at the reaction temperature of 50-120 ℃ for 3-15 hours, continuously adding water for saponification reaction, and refluxing for 1-10 hours to obtain the ionic polyether compound; wherein, Y0Selected from chlorine, bromine or iodine, Z0Is selected from COOR0,R0Is selected from C1～C8Alkyl groups of (a);
(c) uniformly mixing the required amount of the surfactant composition obtained in the step (b) with a polymer and alkali according to the mass parts to obtain the oil-displacing agent;
wherein, the preferred scheme is as follows: the ionizing agent R2Y is preferably at least one of an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid, and an alkali metal salt of chloroacetic acid sulfonating agent, and the alcohol is preferably selected from C1～C4The fatty alcohol of (a); the above-mentioned
And R2The preferred molar ratio of Y is 1: 1-3; the method comprises the following steps: the reaction temperature is preferably 120-160 ℃, the pressure is preferably 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate; the second step is as follows: the alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (0.3-3) to (0.2-6), and Y is preferably 10Preferably one of chlorine or bromine, R0Preferably C1～C4Alkyl group of (1).
10. A method for enhanced oil recovery comprising the steps of:
(1) mixing the composite oil-displacing agent of claim 8 with water to obtain an oil-displacing system;
(2) and contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-150 ℃ and the total salinity is more than 500 mg/L of simulated formation water, and displacing the crude oil in the oil-bearing stratum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910633121.2A CN112225667B (en) | 2019-07-15 | 2019-07-15 | Composite surfactant composition, oil displacement agent, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910633121.2A CN112225667B (en) | 2019-07-15 | 2019-07-15 | Composite surfactant composition, oil displacement agent, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112225667A true CN112225667A (en) | 2021-01-15 |
| CN112225667B CN112225667B (en) | 2023-04-07 |
Family
ID=74111389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910633121.2A Active CN112225667B (en) | 2019-07-15 | 2019-07-15 | Composite surfactant composition, oil displacement agent, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225667B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778515A (en) * | 2021-01-29 | 2021-05-11 | 佛山市华联有机硅有限公司 | Polyether sulfonic acid and solvent-free preparation method and application thereof |
| CN115637142A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Oil displacement agent containing fatty chain and preparation method and application thereof |
| CN115873579A (en) * | 2021-09-29 | 2023-03-31 | 中国石油化工股份有限公司 | Viscosity-reducing washing oil agent for thickened oil and preparation method and application thereof |
| CN116023922A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Surfactant composition, thick oil displacement agent, preparation method and application thereof, and method for improving thick oil recovery rate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060019836A1 (en) * | 2004-06-02 | 2006-01-26 | Fang Li | Multicomponent viscoelastic surfactant fluid and method of using as a fracturing fluid |
| CN103965851A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Composite surfactant and preparation method thereof |
| CN106590587A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Polyether carboxylic acid or salt surfactant-containing composition, preparation method and uses thereof |
-
2019
- 2019-07-15 CN CN201910633121.2A patent/CN112225667B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060019836A1 (en) * | 2004-06-02 | 2006-01-26 | Fang Li | Multicomponent viscoelastic surfactant fluid and method of using as a fracturing fluid |
| CN103965851A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Composite surfactant and preparation method thereof |
| CN106590587A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Polyether carboxylic acid or salt surfactant-containing composition, preparation method and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| ANAT SHILOACH等: "Prediction of Critical Micelle Concentrations and Synergism of Binary Surfactant Mixtures Containing Zwitterionic Surfactants", 《LANGMUIR》 * |
| ERICH ZIEGLER等: "Reactions with betaines. 19. Effect of substituents at the cationic center of betaines on the case of formation of bis(trifluoracetyl) N-ylides", 《MONATSHEFTE FUER CHEMIE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778515A (en) * | 2021-01-29 | 2021-05-11 | 佛山市华联有机硅有限公司 | Polyether sulfonic acid and solvent-free preparation method and application thereof |
| CN112778515B (en) * | 2021-01-29 | 2023-03-14 | 佛山市华联有机硅有限公司 | Polyether sulfonic acid and solvent-free preparation method and application thereof |
| CN115637142A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Oil displacement agent containing fatty chain and preparation method and application thereof |
| CN115637142B (en) * | 2021-07-20 | 2024-04-09 | 中国石油天然气股份有限公司 | Oil displacement agent containing fatty chain and preparation method and application thereof |
| CN115873579A (en) * | 2021-09-29 | 2023-03-31 | 中国石油化工股份有限公司 | Viscosity-reducing washing oil agent for thickened oil and preparation method and application thereof |
| CN115873579B (en) * | 2021-09-29 | 2024-05-03 | 中国石油化工股份有限公司 | Viscous oil viscosity-reducing wash oil agent and preparation method and application thereof |
| CN116023922A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Surfactant composition, thick oil displacement agent, preparation method and application thereof, and method for improving thick oil recovery rate |
| CN116023922B (en) * | 2021-10-26 | 2024-03-26 | 中国石油化工股份有限公司 | Surfactant composition, thick oil displacement agent, preparation method and application thereof, and method for improving thick oil recovery rate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112225667B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112225667B (en) | Composite surfactant composition, oil displacement agent, preparation method and application thereof | |
| CN112708411B (en) | Oil displacement zwitterionic surfactant and polyether amine surfactant composition, and preparation method and application thereof | |
| CN106590590B (en) | Oil displacement composition containing polyether carboxylate surfactant and preparation method thereof | |
| CN106590586B (en) | Oil displacement agent for tertiary oil recovery | |
| CN108314999B (en) | Method for efficiently improving crude oil recovery ratio | |
| CN106867494B (en) | Combined surfactant with strong crude oil solubilizing capability and low-cost preparation method | |
| CN108315001B (en) | High-efficiency oil displacement agent, preparation method and application | |
| CN112226224B (en) | Method for increasing crude oil recovery ratio | |
| CN106867495B (en) | Composite surfactant and low-cost preparation method thereof | |
| RU2647554C2 (en) | Surfactant composition, production and use thereof | |
| CN112708409B (en) | Composition containing amido polyether cationic surfactant and preparation and application thereof | |
| CN112226225A (en) | Temperature-resistant and salt-resistant surfactant composition for pressure reduction and injection increase of water injection well of low-permeability oil reservoir and preparation method and application thereof | |
| CN106593373B (en) | The method that low cost improves oil recovery factor | |
| CN112226226B (en) | Aniline compound and polyether surfactant composition and poly-surface oil displacement agent | |
| CN113930226B (en) | Surfactant composition containing polyether quaternary ammonium salt and preparation method thereof and method for improving oil and gas yield | |
| CN108314997B (en) | Fluid for greatly improving crude oil recovery ratio, preparation method and application | |
| CN109403932B (en) | Oil displacement method for reducing adsorption loss | |
| CN112694880A (en) | Surfactant composition containing aniline compound for oil displacement and preparation method and application thereof | |
| CN113930229B (en) | Oil displacement agent containing quaternary ammonium salt surfactant composition, and preparation method and application thereof | |
| CN106590569B (en) | Enhanced oil recovery method for improving recovery ratio | |
| CN112694878B (en) | Ester-group-containing polyether cationic surfactant composition and preparation and application thereof | |
| CN108316901B (en) | Method for high-efficiency intensified oil production | |
| CN106590598B (en) | Oil displacement composition and preparation method thereof | |
| CN114479811B (en) | Anionic-nonionic surfactant and preparation method and application thereof | |
| CN106590588B (en) | Oil displacement composition for tertiary oil recovery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |