CN114456370B - Polyether anionic surfactant and method for improving oil and gas recovery ratio - Google Patents
Polyether anionic surfactant and method for improving oil and gas recovery ratio Download PDFInfo
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- CN114456370B CN114456370B CN202011243187.XA CN202011243187A CN114456370B CN 114456370 B CN114456370 B CN 114456370B CN 202011243187 A CN202011243187 A CN 202011243187A CN 114456370 B CN114456370 B CN 114456370B
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- polyether
- oil
- surfactant
- anionic surfactant
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 89
- 229920000570 polyether Polymers 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 239000003945 anionic surfactant Substances 0.000 title claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000000732 arylene group Chemical group 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000002091 cationic group Chemical group 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 93
- 239000010779 crude oil Substances 0.000 claims description 28
- 238000006073 displacement reaction Methods 0.000 claims description 26
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 description 85
- 238000006243 chemical reaction Methods 0.000 description 51
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 238000011156 evaluation Methods 0.000 description 33
- -1 heterocyclic hydrocarbon Chemical class 0.000 description 29
- 239000002736 nonionic surfactant Substances 0.000 description 29
- 230000001804 emulsifying effect Effects 0.000 description 20
- 239000011734 sodium Substances 0.000 description 19
- 235000019445 benzyl alcohol Nutrition 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010926 purge Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000006266 etherification reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000011591 potassium Substances 0.000 description 13
- 229910052700 potassium Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 11
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 10
- 230000033558 biomineral tissue development Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000008186 active pharmaceutical agent Substances 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 6
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 6
- 229950009195 phenylpropanol Drugs 0.000 description 6
- 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 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229940050390 benzoate Drugs 0.000 description 5
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000003027 oil sand Substances 0.000 description 4
- 238000005063 solubilization Methods 0.000 description 4
- 230000007928 solubilization Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DKTSRTYLZGWAIT-UHFFFAOYSA-N 1-octadecylnaphthalene Chemical compound C1=CC=C2C(CCCCCCCCCCCCCCCCCC)=CC=CC2=C1 DKTSRTYLZGWAIT-UHFFFAOYSA-N 0.000 description 1
- CEPMBESUVXXFST-UHFFFAOYSA-N 3-chloropropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCl CEPMBESUVXXFST-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003010 ionic group Chemical group 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
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JMPUQZDKYSFZLC-UHFFFAOYSA-N undecane-3-sulfonic acid Chemical compound CCCCCCCCC(CC)S(O)(=O)=O JMPUQZDKYSFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
-
- 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
- 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
- C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a polyether anion surfactant and a method for improving oil and gas recovery ratio, which adopts the polyether anion surfactant, and has a molecular general formula shown in the specification, wherein a substituent R is C 1 ～C 24 Any one of the aliphatic groups of (a); r is R 1 、R 2 、R 3 At least one of H, methyl and ethyl is independently selected; x, y and z are polymerization degrees, and x, y and z are independently selected from any one of 1 to 100; x is any one of alkylene, alkenylene, arylene containing 0 to 10 carbon atoms or alkylene, alkenylene, arylene containing 0 to 10 carbon atoms and containing substituents; y is an anionic group, a is the absolute value of the valence of Y; m is a cation or a cationic group, b is the absolute value of the valence of M; ar is an aromatic ring or a substituent-containing aromatic ring; the technical scheme that m is any integer from 1 to 5 can be used for the enhanced oil recovery process of the oil field.
Description
Technical Field
The invention relates to a polyether anionic surfactant and a method for improving oil and gas recovery ratio.
Background
The thickened oil occupies a large proportion in world oil gas resources,the reserves of the world thick oil, the super thick oil and the natural asphalt are about 1000 multiplied by 10 8 Tons. The Chinese thick oil resource is widely distributed, the thick oil exploitation has great potential, and the proportion of the thick oil exploitation is continuously increased along with the reduction of the light oil exploitation reserves. The medium petrochemical thick oil is rich in resources, and accounts for about 1/3 of the whole country, the dynamic thick oil reserves are mainly concentrated in fields such as victory, northwest, henan and the like, about 21 hundred million tons, the development mode is mainly water flooding and steam injection thermal recovery, and the dynamic thick oil reserves are about 6 hundred million tons. In recent years, the annual yield of medium petrochemical thick oil is basically maintained to be more than 1000 ten thousand tons, and the annual yield of medium petrochemical thick oil accounts for about 1/4 of the total yield of medium petrochemical crude oil. Wherein, the yield ratio of the hot recovery thick oil>40％。
Thickened oils generally have the following significant characteristics: (1) The condensed ring structure in the thick oil has extremely high colloid and asphaltene content, low saturated hydrocarbon and aromatic hydrocarbon content, hydrocarbon content generally less than 60 percent, and a large number of sulfur-containing and nitrogen-containing heterocyclic derivatives, and the relative density and viscosity of the thick oil are correspondingly increased along with the increase of heavy components and impurity components. (2) The temperature has a remarkable effect on the viscosity of the thick oil, and the viscosity of the thick oil is sharply reduced and the fluidity is greatly enhanced along with a certain value of the temperature rise. (3) The thick oil contains more heterocyclic hydrocarbon derivatives containing oxygen, sulfur, nitrogen, phosphorus and other heteroatoms and part of rare metals. (4) the thickened oil has complex rheological properties. Different rheological behavior with increasing temperature, non-newtonian fluids gradually change to newtonian fluids. For heavy oil reservoirs, conventional methods are difficult to produce, so special technological measures such as thermal oil production, chemical oil production, biological oil production, combination methods and the like are adopted. In recent years, chemical methods have received increasing attention. The main difficulties in heavy oil recovery are that the viscosity of crude oil is high, the fluidity of crude oil is poor, and the viscosity of crude oil is high, which causes poor wave and efficiency in the general displacement process of displacement fluid (such as hot water). The solution is to inject surfactant to reduce interfacial tension between crude oil and formation water, so that crude oil is easy to flow; emulsifying the crude oil by the action of a surfactant to form an oil-in-water emulsion, and reducing the viscosity of the crude oil; the wettability of the rock stratum is changed, so that the surface hydrophilicity of the rock stratum is increased. In view of this situation, the development of novel surfactants is of great importance for enhanced recovery of heavy oil.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a novel polyether anionic surfactant which has the advantages of strong emulsifying capacity and high activity on thick oil under the conditions of high temperature and high salt.
The second technical problem to be solved by the invention is to provide a method for improving the oil gas recovery ratio corresponding to one of the technical problems, and the novel polyether anionic surfactant is adopted as an oil displacement agent, so that the method has the advantages of strong emulsifying capacity and high activity on thick oil under the conditions of high temperature and high salt.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a polyether anionic surfactant having the general molecular formula:
wherein the substituent R is C 1 ～C 24 Any one of the aliphatic groups of (a); r is R 1 、R 2 、R 3 At least one of H, methyl and ethyl is independently selected; x, y and z are polymerization degrees, and x, y and z are independently selected from any one of 1 to 100; x is any one of alkylene, alkenylene, arylene containing 0 to 10 carbon atoms or alkylene, alkenylene, arylene containing 0 to 10 carbon atoms and containing substituents; y is an anionic group, a is the absolute value of the valence of Y; m is a cation or a cationic group, b is the absolute value of the valence of M; ar is an aromatic ring or a substituent-containing aromatic ring; m is any integer from 1 to 5.
In the above technical scheme, R is preferably C 1 ～C 20 Any one of alkyl and alkenyl; ar can be benzene ring, condensed ring aromatic ring, benzene ring containing substituent and condensed ring aromatic ring, preferably benzene ring or naphthalene ring; the R is 1 Preferably from ethyl, R 2 Preferably from methyl, R 3 Preferably selected from H.
In the above technical scheme, x, y and z are preferably any number independently selected from 1 to 50.
In the above technical scheme, the linking group X is preferably any one of an alkylene group, an alkenylene group, and an arylene group containing 0 to 6 carbon atoms; when the number of carbon atoms is 0, it means that there is no linking group, and Y is directly linked to Ar.
In the above technical scheme, the Y is preferably any one selected from carboxylate, sulfonate, sulfate and phosphate; more preferably, the compound is any one of carboxylate and sulfonate.
In the above technical solution, the M is preferably any one of alkali metal ions, alkaline earth metal examples and ammonium ions; more preferably M is preferably selected from Na + 、K + 、Mg 2+ 、Ca 2+ 、NH 4 + Any one of the following.
In the above technical scheme, the preparation method of the polyether anionic surfactant preferably comprises the following steps:
a) Carrying out alkoxylation reaction on an initiator and ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst to obtain polyether; wherein the initiator is C as substituent 1 ～C 30 Any one of fatty-based aromatic alcohols;
b) Polyether sulfonate which is the polyether anionic surfactant can be obtained by the polyether synthesized in the step a) through sulfonation reaction or alkylation reaction;
or:
c) And c), reacting the polyether synthesized according to the step a) with an etherification reagent to obtain polyether carboxylate, namely the polyether anionic surfactant.
In the technical scheme, the reaction temperature of the alkoxylation reaction is preferably 140-200 ℃, and the reaction pressure is preferably 0-5 MPa; the molar ratio of the initiator to the ethylene oxide, propylene oxide or butylene oxide is preferably 1 (1-50); the catalyst is preferably an alkali metal hydroxide, DMC bimetallic polyether catalyst or phosphazene catalyst, and the dosage is 0.001-2.0% of the weight of the starter.
In the above technical scheme, the molar ratio of the polyether to the sulfonating agent is preferably 1: (1-3), the reaction temperature of the sulfonation reaction is preferably 20-80 ℃, the sulfonation reaction time is preferably 0.5-10 hours, the pH after adding alkali is 10-14, and the hydrolysis reaction time is 0.5-5 hours.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: a method for improving oil and gas recovery ratio adopts any one of the polyether anionic nonionic surfactants in one of the technical schemes for solving the technical problems as an oil displacement agent.
In the above technical solution, the method is not particularly limited, and a person skilled in the art may use the polyether anionic nonionic surfactant as an oil displacement agent according to the existing technology, for example, the aqueous solution containing the surfactant of the present invention is injected into the ground to improve the recovery efficiency of an oil-gas field, and the use concentration of the surfactant is preferably 0.05w.t.% or more.
In the above technical solution, it is further preferable that the oil is a thick oil, and the method for improving oil and gas recovery efficiency is especially a method for improving thick oil recovery efficiency.
The polyether anionic nonionic surfactant disclosed by the invention simultaneously comprises aryl and composite polyether functional groups (polyoxybutylene BO, polyoxypropylene PO and polyoxyethylene EO) in the molecular structure, so that the interaction with crude oil is enhanced, particularly the interaction with a thickened oil component is enhanced, the technical problems of poor emulsifying property and low activity of the surfactant in the existing enhanced oil recovery technology are solved, and the oil displacement effect can be effectively improved.
The polyether anionic nonionic surfactant is used in tertiary oil recovery, especially for heavy oil reservoirs (such as more than 90 ℃, more than 35,000mg/L of mineralization degree and more than 1,000mg/L of divalent ion content), and has the following advantages:
(1) The surfactant has high interfacial activity on thickened oil and strong emulsifying capacity. It can form 10 with underground crude oil at a concentration of above 0.05% -3 ～10 -4 The ultra-low interfacial tension of milli-newtons per meter and the solubilization parameters reach above 10.
(2) The temperature resistance and the salt resistance are strong. The salt resistance of the anti-salt agent is obviously improved because the anti-salt agent contains non-ionic groups such as BO, PO, EO and the like; and different functional groups are connected through a C-C bond or a C-O bond, so that the hydrothermal stability of the compound is high.
(3) The surfactant has good safety. The surfactant is more environment-friendly because the alcohol is adopted to replace phenol as the initiator.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Synthesis of octadecyl naphthalene methanol polyether ammonium sulfonate anionic nonionic surfactant:
adding a certain amount of octadecyl naphthaline methyl alcohol, 0.5% KOH and 30ppm phosphazene catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the alkylaryl polyether nonionic surfactant.
Introducing sulfonating agent SO into the product 3 Sulfonation was carried out at 60℃for 1 hour. Then adding 3 times of potassium hydroxide aqueous solution with molar weight into a reactor, starting stirring, and hydrolyzing at 90 ℃ for 5 hours to obtain the product of the octadecyl naphthalene methanol polyether potassium sulfonate anionic non-surfactant. The product was dissolved in an ethanol/water (V/v=7:3) mixed solution and passed through an acidic ion exchange column, then the octadecyl naphthalene methanol polyether sulfonic acid was neutralized with aqueous ammonia, and the solvent was distilled off under reduced pressure after heating to 100 ℃ to obtain ammonium octadecyl naphthalene methanol polyether sulfonic acid, the structure of which is shown in table 1.
Active concentration window assay:
the prepared octadecyl naphthalene methanol polyether ammonium sulfonate surfactant was formulated into different concentrations (mineralization degree of water used 35,000mg/L, divalent ion content 1,000 mg/L), and the interfacial tension change between the surfactant solution and crude oil (crude oil api=25) was measured at 90 ℃ under the condition of 5000 rpm using a TX-500C rotary drop interfacial tensiometer or Dataphysics SVT20 until the oil drops were balanced, and the results are shown in table 2.
TABLE 2 interfacial tension between oil and water of surfactant solutions of different concentrations and crude oil
| Surfactant dosage (wt%) | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (milli-newtons per meter) | 0.00293 | 0.00087 | 0.00055 | 0.00042 |
The results show that the surfactant provided by the invention has high oil-water interfacial activity on the tested thickened oil under a wide concentration window.
Evaluation of emulsifying property of surfactant:
the emulsification capacity was calculated by evaluating the phase state according to SPE 113313 method. The method mainly comprises the following steps: an aqueous surfactant solution having a concentration of 0.3wt% was added to the glass tube, and then crude oil was added to the solution with a water-to-oil volume ratio (WOR) of 1.0. And mixing after sealing. It is then placed in a metal bath, heated to a set temperature, and the sample mixture is periodically removed to enhance mass transfer between the phases. The equilibrium was considered to be reached until there was no change in visual interface position. Its emulsifying capacity is expressed in terms of the solubilization parameter SP, i.e., the volume or mass of surfactant per unit volume or mass of water in or of oil. The results are shown in tables 3 and 4.
Surfactant interfacial property evaluation:
the interfacial tension change between the 0.3wt% surfactant solution and crude oil was measured using a TX-500C spin drop interfacial tensiometer or DataPhysics SVT20 at a reservoir temperature and a rotational speed of 5000 rpm until the oil drops equilibrated. The results are shown in tables 5 and 6.
Evaluation of surfactant wash oil Performance
Taking a certain amount of oil sand according to the following oil: sand=1: 4 (mass ratio) aging for 10 days at reservoir temperature, stirring for 5 minutes every 2 hours; and then taking out 5g of the aged oil sand, and mixing the aged oil sand with 0.3wt% of surfactant solution according to the weight percentage of the oil sand: solution mass ratio = 1:10, aging for 48 hours at the reservoir temperature, extracting crude oil in the solution by using petroleum ether, fixing the volume by using a 50ml colorimetric tube, and performing colorimetric analysis at a wavelength of 430nm by using a spectrophotometer. The concentration of crude oil in the surfactant solution was calculated using a standard curve. The results are shown in tables 7 and 8.
Evaluation of oil displacement performance of surfactant
According to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method, a simulated oil displacement experiment is carried out at the oil reservoir temperature. The oil recovery rate of the crude oil is calculated by injecting water to drive the oil to be free, then transferring 0.3PV (core pore volume) of the surfactant solution with the weight percent of 0.3, and then driving the water to be free of oil again. The results are shown in tables 9 and 10.
[ example 2 ]
Synthesis of nonylbenzyl alcohol polyether calcium carboxylate anionic surfactant:
adding a certain amount of 4-nonyl 2-hydroxymethylbenzene propionic acid and 1% KOH (potassium hydroxide) serving as a catalyst in a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging a system with nitrogen to remove unreacted ethylene oxide to obtain the 4-nonyl-2-hydroxymethyl polyether benzene potassium propionate anionic nonionic surfactant. The product was dissolved in an ethanol/water (V/v=7:3) mixed solution and passed through an acidic ion exchange column, then 4-nonyl-2-hydroxypolyether phenylpropionic acid was neutralized with an aqueous solution of calcium hydroxide, the temperature was raised to 100 ℃ and the solvent was distilled off under reduced pressure to give calcium 4-nonyl-2-hydroxypolyether phenylpropionate, and the structure was as shown in table 1.
Evaluation of emulsifying property of surfactant:
the emulsifying properties of the calcium 4-nonyl-2-hydroxymethyl polyether phenylpropionate surfactant were measured according to the method and procedure described in example 1. The results are shown in tables 3 and 4.
Surfactant interfacial property evaluation:
the interfacial properties of the calcium 4-nonyl-2-hydroxymethyl polyether phenylpropionate surfactant were determined according to the method and procedure described in example 1. The results are shown in tables 5 and 6.
Evaluation of surfactant wash oil Performance
The wash oil performance of the calcium 4-nonyl-2-hydroxymethyl polyether phenylpropionate surfactant was determined according to the procedure and procedure described in example 1. The results are shown in tables 7 and 8.
Evaluation of oil displacement performance of surfactant
The displacement performance of the calcium 4-nonyl-2-hydroxymethyl polyether phenylpropionate surfactant was measured according to the method and procedure described in example 1. The results are shown in tables 9 and 10.
[ example 3 ]
Synthesis of pentadecyl benzyl alcohol polyether magnesium sulfonate anionic nonionic surfactant:
pentadecyl benzyl alcohol, 2.0% KOH and 30ppm phosphazene catalyst are added into a polymerization reaction kettle, the system temperature is heated to 80-90 ℃ under stirring, a vacuum system is started for dehydration for 1 hour, nitrogen is used for purging 3-4 times to remove air in the system, then the reaction temperature is raised to 180 ℃, then metered epoxybutane is slowly introduced, and the reaction pressure is controlled to be less than 0.60MPa for etherification reaction. And after the reaction is finished, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, adding calculated amount of ethylene oxide again, cooling to 150 ℃, and carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the pentadecyl benzyl alcohol polyether nonionic surfactant.
Introducing sulfonating agent SO into the product 3 Sulfonation was carried out at 60℃for 1 hour. Then adding aqueous solution of potassium hydroxide with 3 times of molar quantity into a reactor, starting stirring, and hydrolyzing for 5 hours at 90 ℃ to obtain the product pentadecyl benzyl alcohol polyether potassium sulfonate anionic non-surfactant. The product was dissolved in an ethanol/water (V/v=7:3) mixed solution and passed through an acidic ion exchange column, then pentadecyl benzyl alcohol polyether sulfonic acid was neutralized with an equimolar amount of aqueous solution of magnesium hydroxide, and after heating to 100 ℃ and steaming out the solvent under reduced pressure, pentadecyl benzyl alcohol polyether sulfonic acid magnesium was obtained, and the structure is shown in table 1.
Evaluation of emulsifying property of surfactant:
the emulsification properties of the pentadecyl benzyl alcohol polyether magnesium sulfonate surfactant were determined according to the procedure and procedure in example 1. The results are shown in tables 3 and 4.
Surfactant interfacial property evaluation:
the interfacial properties of the pentadecyl benzyl alcohol polyether sulfonate magnesium surfactant were determined according to the procedure and procedure in example 1. The results are shown in tables 5 and 6.
Evaluation of surfactant wash oil Performance
The wash oil performance of the pentadecyl benzyl alcohol polyether magnesium sulfonate surfactant was determined according to the procedure and procedure in example 1. The results are shown in tables 7 and 8.
Evaluation of oil displacement performance of surfactant
The oil displacement performance of the pentadecyl benzyl alcohol polyether magnesium sulfonate surfactant was determined according to the method and procedure in example 1. The results are shown in tables 9 and 10.
[ example 4 ]
Synthesis of sodium methyl benzyl alcohol polyether sulfonate anionic nonionic surfactant:
adding a certain amount of methylbenzyl alcohol and 0.5% KOH (potassium hydroxide) serving as a catalyst in a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing metered epoxybutane after the reaction temperature is raised to 200 ℃, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the alkylaryl polyether nonionic surfactant.
Introducing sulfonating agent SO into the product 3 Sulfonation was carried out at 60℃for 1 hour. Then adding aqueous solution of sodium hydroxide with 3 times of molar quantity into a reactor, starting stirring, hydrolyzing for 5 hours at 90 ℃, heating to 100 ℃, decompressing and distilling off the solvent, and filtering to remove salt to obtain the product of the sodium methylbenzyl alcohol polyether sulfonate anionic surfactant. The structure is shown in Table 1.
Evaluation of emulsifying property of surfactant:
the emulsifying properties of sodium methylbenzyl alcohol polyether sulfonate anionic non-surfactant were measured according to the method and procedure in example 1. The results are shown in tables 3 and 4.
Surfactant interfacial property evaluation:
the interfacial properties of sodium methylbenzyl alcohol polyether sulfonate anionic non-surfactant were determined according to the methods and procedures described in example 1. The results are shown in tables 5 and 6.
Evaluation of surfactant wash oil Performance
The wash oil performance of sodium methylbenzyl alcohol polyether sulfonate anionic non-surfactant was measured according to the method and procedure in example 1. The results are shown in tables 7 and 8.
Evaluation of oil displacement performance of surfactant
The displacement performance of sodium methylbenzyl alcohol polyether sulfonate anionic non-surfactant was measured according to the method and procedure in example 1. The results are shown in tables 9 and 10.
[ example 5 ]
Synthesis of sodium octyl benzyl alcohol polyether sulfonate anionic nonionic surfactant:
adding a certain amount of octyl benzyl alcohol and 0.5% KOH catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing metered epoxybutane after the reaction temperature is raised to 200 ℃, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the alkylaryl polyether nonionic surfactant.
Adding formyl chloride with the same molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction, stirring and heating to 80 ℃, slowly dropwise adding 3-chloropropanesulfonic acid, continuing the reaction for 5 hours after the addition, and obtaining octyl (propane sulfonic acid) benzyl alcohol polyether formate through aftertreatment. Adding 2 times molar quantity of aqueous solution of sodium hydroxide into the reactant, heating to 80 ℃, stirring for 6 hours, adding solvent benzene, refluxing to remove water, and filtering to remove solid in the reactant to obtain the product octyl benzyl alcohol polyether sodium sulfonate anionic nonionic surfactant. The structure is shown in Table 1.
Evaluation of emulsifying property of surfactant:
the emulsification properties of the sodium octyl benzyl polyether sulfonate anionic nonionic surfactant were determined as described in example 1. The results are shown in tables 3 and 4.
Surfactant interfacial property evaluation:
the interfacial properties of the sodium octyl benzyl polyether sulfonate anionic nonionic surfactant were determined according to the methods and procedures described in example 1. The results are shown in tables 5 and 6.
Evaluation of surfactant wash oil Performance
The wash oil performance of the sodium octyl benzyl polyether sulfonate anionic nonionic surfactant was determined as described in example 1. The results are shown in tables 7 and 8.
Evaluation of oil displacement performance of surfactant
The displacement performance of the sodium octyl benzyl polyether sulfonate anionic nonionic surfactant was determined according to the method and procedure described in example 1. The results are shown in tables 9 and 10.
[ example 6 ]
Synthesis of alkylaryl (potassium sulfonate) polyether nonionic surfactant:
adding a certain amount of dodecyl benzyl alcohol, 1% KOH and 30ppm phosphazene catalyst in the mass percent into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, and controlling the reaction pressure to be less than 2.0MPa for etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amounts of propylene oxide and ethylene oxide in sequence, cooling to 150 ℃ after the reaction is finished, and removing unreacted ethylene oxide by using a nitrogen purging system to obtain the octadecyl aryl polyether nonionic surfactant.
Subjecting the product obtained above to SO 3 Sulfonation is carried out, reaction is carried out for 1 hour at 50 ℃, then potassium hydroxide is added to adjust the pH to 13, hydrolysis is carried out for 2 hours, and dodecyl aryl (potassium sulfonate) polyether is obtained. The structure is shown in Table 1.
Evaluation of emulsifying property of surfactant:
the emulsification properties of the dodecylaryl (potassium sulfonate) polyether surfactant were determined according to the methods and procedures described in example 1. The results are shown in Table 3.
Surfactant interfacial property evaluation:
the interfacial properties of the dodecylaryl (potassium sulfonate) polyether surfactant were determined according to the methods and procedures described in example 1. The results are shown in Table 5.
Evaluation of surfactant wash oil Performance
The wash oil performance of the dodecylaryl (potassium sulfonate) polyether surfactant was determined following the procedure and procedure in example 1. The results are shown in Table 7.
Evaluation of oil displacement performance of surfactant
The flooding performance of the dodecylaryl (potassium sulfonate) polyether surfactant was determined following the procedure and procedure in example 1. The results are shown in Table 9.
[ example 7 ]
Synthesis of octadecyl aryl (sodium sulfonate) polyether nonionic surfactant:
adding a certain amount of octadecyl benzyl alcohol, 1% KOH and 30ppm phosphazene catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, and controlling the reaction pressure to be less than 2.0MPa for etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amounts of epoxybutane, epoxypropane and epoxyethane in sequence, cooling to 150 ℃ after the reaction is finished, and removing unreacted epoxy compounds by using a nitrogen purging system to obtain the octadecyl aryl polyether nonionic surfactant.
Subjecting the product obtained above to SO 3 Sulfonation is carried out, reaction is carried out for 1 hour at 50 ℃, then sodium hydroxide is added to adjust the pH to 13, hydrolysis reaction is carried out for 2 hours to neutrality, and octadecyl aryl (sodium sulfonate) polyether is obtained. The structure is shown in Table 1.
Evaluation of emulsifying property of surfactant:
the emulsifying properties of the octadecyl aryl (sodium sulfonate) polyether surfactant were determined according to the method and procedure in example 1. The results are shown in Table 3.
Surfactant interfacial property evaluation:
the interfacial properties of the octadecyl aryl (sodium sulfonate) polyether surfactant were determined according to the methods and procedures described in example 1. The results are shown in Table 5.
Evaluation of surfactant wash oil Performance
The wash oil performance of the octadecyl aryl (sodium sulfonate) polyether surfactant was determined following the procedure and procedure in example 1. The results are shown in Table 7.
Evaluation of oil displacement performance of surfactant
The oil displacement performance of the octadecyl aryl (sodium sulfonate) polyether surfactant was determined following the procedure and procedure described in example 1. The results are shown in Table 9.
[ example 8 ]
Synthesis of octadecyl (potassium 4-benzoate) phenylpropanol polyether nonionic surfactant:
adding a certain amount of octadecyl (4-benzoyl) phenylpropanol and 2% KOH and 30ppm phosphazene catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing metered epoxybutane after the reaction temperature is raised to 200 ℃, and controlling the reaction pressure to be less than 2.0MPa for etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amounts of epoxybutane, epoxypropane and epoxyethane in sequence, cooling to 150 ℃ after the reaction is finished, and removing unreacted epoxy compounds by using a nitrogen purging system to obtain the octadecyl (4-potassium benzoate) phenylpropanol polyether nonionic surfactant. The structure is shown in Table 1.
Evaluation of emulsifying property of surfactant:
the emulsifying properties of the octadecyl (potassium 4-benzoate) phenylpropanol polyether nonionic surfactant were measured in accordance with the method and procedure of example 1. The results are shown in Table 3.
Surfactant interfacial property evaluation:
the interfacial properties of the octadecyl (potassium 4-benzoate) phenylpropanol polyether nonionic surfactant were measured according to the method and procedure in example 1. The results are shown in Table 5.
Evaluation of surfactant wash oil Performance
The wash oil performance of the octadecyl (potassium 4-benzoate) phenylpropanol polyether nonionic surfactant was measured according to the method and procedure in example 1. The results are shown in Table 7.
Evaluation of oil displacement performance of surfactant
The displacement performance of the octadecyl (potassium 4-benzoate) phenylpropanol polyether nonionic surfactant was measured according to the method and procedure of example 1. The results are shown in Table 9.
[ comparative example 1 ]
Polyether anionic nonionic surfactant was prepared as in example 1 except that propylene oxide and butylene oxide were not added, and performance evaluation was performed as in example 1, and the results are shown in tables 3 to 10.
[ comparative example 2 ]
Preparation of surfactant C according to the method of US20110281779A1 8 H 17 O-(BO) 7 -(PO) 7 -(EO) 25 -SO 3 Na and performance was evaluated as in example 1, and the results are shown in tables 3 to 10.
TABLE 1 surfactant compositions and structures
TABLE 3 emulsifying Properties of surfactants
Test conditions: 90 ℃, mineralization degree 35,000mg/L, divalent ion content 1,000mg/L, crude oil API=25
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Comparative example 1 | Comparative example 2 |
| Solubilization parameters | 15 | 12 | 13 | 11 | 10 | 13 | 12 | 9 | 6 | 7 |
TABLE 4 emulsifying Properties of surfactants
Test conditions: 120 ℃, mineralization degree 300,000mg/L, divalent ion content 10,000mg/L, crude oil API=18
| Examples | 1 | 2 | 3 | 4 | 5 | Comparative example 1 | Comparative example 2 |
| Solubilization parameters | 17 | 14 | 14 | 13 | 11 | 7 | 7 |
TABLE 5 interfacial surfactant properties
Test conditions: 90 ℃, mineralization degree 35,000mg/L, divalent ion content 1,000mg/L, crude oil API=25
TABLE 6 interfacial surfactant properties
Test conditions: 120 ℃, mineralization degree 300,000mg/L, divalent ion content 10,000mg/L, crude oil API=18
| Examples | 1 | 2 | 3 | 4 | 5 | Comparative example 1 | Comparative example 2 |
| Interfacial tension (10) -3 mN/m) | 0.36 | 1.91 | 0.71 | 4.16 | 3.01 | 21.57 | 4.26 |
TABLE 7 surfactant wash oil Performance
Test conditions: 90 ℃, mineralization degree 35,000mg/L, divalent ion content 1,000mg/L, crude oil API=25
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Comparative example 1 | Comparative example 2 |
| Wash oil performance (%) | 80 | 65 | 71 | 62 | 61 | 69 | 72 | 66 | 32 | 51 |
Table 8 surfactant wash performance
Test conditions: 120 ℃, mineralization degree 300,000mg/L, divalent ion content 10,000mg/L, crude oil API=18
| Examples | 1 | 2 | 3 | 4 | 5 | Comparative example 1 | Comparative example 2 |
| Wash oil performance (%) | 82 | 71 | 73 | 63 | 64 | 32 | 50 |
TABLE 9 surfactant oil displacement Properties
Test conditions: 90 ℃, mineralization degree of 35,000mg/L, divalent ion content of 1,000mg/L, crude oil API=25, core permeability of 220mD
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Comparative example 1 | Comparative example 2 |
| Enhanced recovery (%) | 13.9 | 9.1 | 11.1 | 8 | 7.9 | 9.3 | 11.2 | 9.2 | 4.2 | 6.5 |
Table 10 surfactant flooding performance
Test conditions: 120 ℃, mineralization degree 300,000mg/L, divalent ion content 10,000mg/L, crude oil API=18, core permeability 500mD
| Examples | 1 | 2 | 3 | 4 | 5 | Comparative example 1 | Comparative example 2 |
| Enhanced recovery (%) | 14.4 | 9.9 | 13.3 | 8.4 | 8.6 | 4.3 | 6.3 |
The results show that the surfactant provided by the invention has very high oil-water interfacial activity and washing capacity for the tested thickened oil, and has a good effect of improving the recovery ratio of the thickened oil.
Claims (10)
1. A polyether anionic surfactant having the general molecular formula:
；
wherein the substituent R is C 8 ～C 18 Any one of the alkyl groups of (a); r is R 1 Selected from ethyl, R 2 Selected from methyl, R 3 Selected from H; x, y and z are polymerization degrees, x is independently selected from any one of 1-50, y is independently selected from any one of 8-50, and z is independently selected from any one of 1-50; x is any one of an alkylene group, an alkenylene group, an arylene group having 0 to 10 carbon atoms, or an alkylene group, an alkenylene group, or an arylene group having 0 to 10 carbon atoms; y is an anionic group, a is the absolute value of the valence of Y; m is a cation or a cationic group, b is the absolute value of the valence of M; ar is benzene ring, condensed ring aromatic ring, substituent-containing benzene ring or substituent-containing condensed ring aromatic ring; m is any integer from 1 to 5.
2. The polyether anionic surfactant according to claim 1, characterized in that Ar is a benzene ring or a naphthalene ring.
3. The polyether anionic surfactant according to claim 1, wherein Y is any one selected from carboxylate, sulfonate, sulfate, phosphate.
4. A polyether anionic surfactant according to claim 3 characterised in that Y is selected from any one of carboxylate and sulfonate.
5. The polyether anionic surfactant according to claim 1, wherein M is any one of alkali metal ion, alkaline earth metal ion, and ammonium ion.
6. The polyether anionic surfactant according to claim 5, wherein M is selected from Na + 、K + 、Mg 2+ 、Ca 2 + 、NH 4 ＋ Any one of the following.
7. A method for improving crude oil recovery efficiency, which is characterized in that the polyether anionic surfactant according to any one of claims 1-6 is adopted as an oil displacement agent.
8. The method for enhanced oil recovery according to claim 7, wherein the aqueous solution containing the polyether anionic surfactant according to any one of claims 1 to 6 is injected into a hydrocarbon-bearing formation to displace hydrocarbon.
9. The method of enhanced oil recovery according to claim 8, wherein the polyether anionic surfactant is used at a concentration of 0.05w.t.% or more.
10. The method for increasing crude oil recovery according to any one of claims 7 to 8, wherein the oil is a thick oil.
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| CN103003385A (en) * | 2010-04-16 | 2013-03-27 | 德克萨斯州立大学董事会 | Guerbet alcohol alkoxylate surfactants and their use in enhanced oil recovery applications |
| CN103666430A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Surfactant composition for intensifying oil extraction and preparation method thereof |
| WO2014201854A1 (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Surfactant composition, and manufacturing method and application of same |
| CN104232044A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Composite surface active agent composition for tertiary oil recovery and preparation method and application thereof |
| WO2016023139A1 (en) * | 2014-08-12 | 2016-02-18 | 中国石油化工股份有限公司 | Surfactant composition and preparation method therefor and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103003385A (en) * | 2010-04-16 | 2013-03-27 | 德克萨斯州立大学董事会 | Guerbet alcohol alkoxylate surfactants and their use in enhanced oil recovery applications |
| CN103666430A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Surfactant composition for intensifying oil extraction and preparation method thereof |
| WO2014201854A1 (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Surfactant composition, and manufacturing method and application of same |
| CN104232044A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Composite surface active agent composition for tertiary oil recovery and preparation method and application thereof |
| WO2016023139A1 (en) * | 2014-08-12 | 2016-02-18 | 中国石油化工股份有限公司 | Surfactant composition and preparation method therefor and application thereof |
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