CN106590582A - Salt-resistant and oil-displacement surfactant and preparation method thereof - Google Patents
Salt-resistant and oil-displacement surfactant and preparation method thereof Download PDFInfo
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- CN106590582A CN106590582A CN201510683698.6A CN201510683698A CN106590582A CN 106590582 A CN106590582 A CN 106590582A CN 201510683698 A CN201510683698 A CN 201510683698A CN 106590582 A CN106590582 A CN 106590582A
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- sulfonic acid
- salt
- added
- oil displacement
- oil
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 74
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 68
- 150000003839 salts Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 217
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 143
- 238000006243 chemical reaction Methods 0.000 claims description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- -1 alkyl phenol Chemical compound 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 14
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract 2
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract 2
- 230000033558 biomineral tissue development Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 174
- 239000003921 oil Substances 0.000 description 99
- 229910052757 nitrogen Inorganic materials 0.000 description 87
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 84
- 230000018044 dehydration Effects 0.000 description 55
- 238000006297 dehydration reaction Methods 0.000 description 55
- 238000010992 reflux Methods 0.000 description 55
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 238000006386 neutralization reaction Methods 0.000 description 30
- 238000001816 cooling Methods 0.000 description 29
- 239000007789 gas Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 28
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 238000009833 condensation Methods 0.000 description 17
- 230000005494 condensation Effects 0.000 description 17
- 238000007046 ethoxylation reaction Methods 0.000 description 15
- 239000012046 mixed solvent Substances 0.000 description 15
- 230000002194 synthesizing effect Effects 0.000 description 15
- 238000010926 purge Methods 0.000 description 14
- 125000001400 nonyl 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])[H] 0.000 description 12
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 8
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 8
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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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
-
- 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
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
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- 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
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- 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
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- 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
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
- C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
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- 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
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Abstract
The invention relates to a salt-resistant and oil-displacement surfactant and a preparation method thereof and mainly solves the problem of low oil displacement efficiency of surfactants under the high mineralization degree condition in the prior art. According to the technical scheme, the salt-resistant and oil-displacement surfactant named 3-(alkyl phenol polyoxyethylene ether)-2-(hydroxypropyl sulfonate polyoxyethylene ether)propanesulfonate with the structure shown in formula (I), wherein M1 and M2 are independently selected from any one of alkali metals and alkaline earth metals, when M1 is alkali metal, n1 is 1, when M1 is alkaline earth metal, n1 is 0.5, when M2 is alkali metal, n2 is 1, when M2 is alkaline earth metal, n2 is 0.5, R is C4-C20 alkyls, x ranges from 1 to 20, and y ranges from 1 to 10, so that the problem is better solved, and the surfactant can be applied to enhanced oil recovery production of oil fields.
Description
Technical field
The present invention relates to a kind of salt tolerant oil displacement surfactant and preparation method thereof.
Background technology
Oil field enter high water-cut stage after, remaining oil with discontinuous oil film by trap in the hole of reservoir rockses, effect
Two main power on oil droplet are viscaps, if from suitable surfactant system, reducing oil
Interfacial tension between water, makes the interfacial tension between oil reservoirs profit be down to relatively low or ultralow value (10 from 20～30mN/m-3~
10-4MN/m), just can reduce oil droplet when moving remaining oil and deform brought resistance, so as to greatly improve oil displacement efficiency.
The oil refining accessory substance such as the most or petroleum sulfonate of oil recovery surfactant application, heavy alkylbenzene sulfonate is modified
Surfactant, be the characteristics of this kind of surfactant draw materials it is extensive, cheap, but, this kind of surfactant
There is also performance to be not sufficiently stable, salt tolerant especially the poor-performing of resistance to bivalent cation a series of problems, such as, it is impossible to suitable for height
Temperature, the oil field block of high salt.The novel surfactant of multiple active function groups is introduced in same molecule, can be significantly
Improve surface-active.Especially for the higher oil reservoir of salinity, multiple anion head bases can increase hydrophily, improve
The solvability of surfactant, EO, PO group contributes to heightening the anticalcium magnesium ability of surfactant.Patent U.S.
Pat.No.4436672A alkylols obtain alkylol polyglycidyl ether with glycidol reaction, then carry out sulfonation,
Obtain a kind of anion-nonionic surfactant；Patent U.S.Pat.No.4466891A provides a kind of alkyl phenol polyoxy second
Alkene ether propane sulfonic acid salt；Patent U.S.Pat.No.2011015111A1 is contained with alhpa olefin 2- propyl alcohol reaction generation chloro- with 1,3- bis-
There is the ether of chloro base, then carry out sulfonating reaction, obtain a kind of new anion surfactant containing two sulfo groups.
But, existing surfactant has much room for improvement in the oil displacement efficiency of high salt high temperature oil reservoir.
The content of the invention
One of the technical problem to be solved is that surfactant has drive under high temperature, high salt conditions in prior art
A kind of low problem of oily efficiency, there is provided new salt tolerant oil displacement surfactant, the surfactant has in high salinity bar
The characteristics of oil displacement efficiency is high under part.
The two of the technical problem to be solved are to provide a kind of salt tolerant corresponding with one of technical problem is solved and drive
The preparation method of oil meter face activating agent.
The three of the technical problem to be solved are that one of technical problem surfactant improves crude oil in oil field
Application in recovery ratio.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：Salt tolerant oil displacement surfactant, its
Entitled 3- (alkyl phenol polyethenoxy ether) -2- (hydroxypropyl sulfonic acid APEO) propane sulfonic acid salt, structure such as formula (I)
It is shown：
Wherein M1And M2Be independently selected from in alkali metal, alkaline-earth metal any one, work as M1For alkali metal when n1For 1,
Work as M1For alkaline-earth metal when n1For 0.5, work as M2For alkali metal when n2For 1, work as M2For alkaline-earth metal when n2For 0.5,
R is C4～C20Alkyl, x=1～20, y=1～10.
In above-mentioned technical proposal, preferred x=2～8, y=2～8.
In above-mentioned technical proposal, the alkyl is preferably C7～C10Alkyl.
In above-mentioned technical proposal, as the most preferred technical scheme：The alkyl is C8～C9Alkyl, x=4～6,
Y=2-3.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：One of above-mentioned technical problem is described resistance to
The preparation method of salt oil displacement surfactant, comprises the following steps：
A) under base catalyst effect, alkyl phenol obtains alkyl phenol polyethenoxy ether with aequum reacting ethylene oxide；
Reaction temperature is preferably 85～160 DEG C, and pressure is preferably 0～0.40MPa (gauge pressure), and the reaction time is preferably 1～10
Hour；
B) step a) gained alkyl phenol polyethenoxy ethers are dissolved into into C6～C8In aromatic hydrocarbons, add alkali metal hydroxide or
At least one alkali in alkaline earth metal hydroxide, alkalizes 0.5～3 hour at 30～60 DEG C, adds 3- chlorine-2-hydroxyls
The alkali metal salt of propane sulfonic acid, the lower reaction of stirring obtains 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt；The hydrocarbon
Base phenol polyethenoxy ether is preferably 1 with the mol ratio of the alkali:(1～3)；Wherein described alkyl phenol polyethenoxy ether and 3- chlorine
The mol ratio of -2- hydroxy-propanesulfonic acid alkali metal salts is preferably 1:(1～4)；Reaction temperature is preferably 30～80 DEG C；Reaction time
Preferably 6～18 hours；
C) by step b) gained 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt, in base catalyst effect
Under, obtain the 3- (alkyl phenol polyethenoxy ether) -2- (APEO) propane sulfonic acid with aequum reacting ethylene oxide
Salt；Reaction temperature is preferably 85～160 DEG C；Reaction pressure is preferably 0～0.40MPa (gauge pressure)；Reaction time is preferred
1～10 hour；
D) by step c) gained 3- (alkyl phenol polyethenoxy ether) -2- (APEO) propane sulfonic acid salt, it is dissolved into
C6～C8In aromatic hydrocarbons, alkali metal hydroxide or at least one alkali in alkaline earth metal hydroxide are added, at 30～60 DEG C
Lower alkalization 0.5～3 hour, adds the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid, the lower reaction of stirring to obtain 3- (alkyl phenol
APEO) -2- (hydroxypropyl sulfonic acid APEO) propane sulfonic acid salt；3- (alkyl the phenol polyethenoxy ether) -2-
(APEO) propane sulfonic acid salt is preferably 1 with the mol ratio of the alkali:(1～3)；3- (the alkyl phenol polyethenoxies
Ether) mol ratio of alkali metal salt of -2- (APEO) propane sulfonic acid salt and 3- chlorine-2-hydroxyl propane sulfonic acid is preferably 1:(1～
4)；Reaction temperature is preferably 30～80 DEG C；Reaction time is preferably 6～18 hours.
In above-mentioned technical proposal, step a) and/or step c) the base catalyst preferred alkali metal hydroxides or alkaline earth
At least one in metal hydroxides.Step b) the alkyl phenol polyethenoxy ethers and 3- chlorine-2-hydroxyl propane sulfonic acid alkali gold
The mol ratio of category salt is more preferably 1:(1～2), the reaction time is more preferably 6～10 hours.Step a) and/or step
C) at least one in the base catalyst more preferably NaOH or potassium hydroxide.Step a) and/or step c) institutes
State reaction temperature and be more preferably 120～140 DEG C, the reaction time is more preferably 6～8 hours.
To solve the three of present invention problem, the technical solution used in the present invention is as follows：One of above-mentioned technical problem is described
Application of the surfactant in oil recovery factor is improved.
In above-mentioned technical proposal, the concrete grammar of the application can be by terms of parts by weight including present invention problem
One of 100～2000 parts of 1 part of the surfactant and water oil displacement agent injection oil bearing bed.The water for wherein adopting can be with
It is deionized water, river, underground water, seawater, preferably total salinity scope is 80000-300000mg/L, Ca2++Mg2+
For the water of 1000-6000mg/L, for the consideration of the aspects such as easy construction, saving water resource, more preferably oil field is injected
The Zhongyuan Oil Field Pu Chengxi Districts injection water that water, such as embodiment of the present invention are adopted.In order to increase oil displacement efficiency, the present invention drives
Additive commonly used in the art, such as small molecule alcohol, DMSO, diethanol amine, CTAC can also be included in finish
Deng.
The key problem in technology of the present invention is that surfactant employs new anion-nonionic surfactant, containing multiple
Hydrophilic radical, two sulfonic acid groups are located at respectively the centre of molecule segment and polyoxyethylene and polyoxyethylene segment.While by
The salt resistance of surfactant and the performance of anti-bivalent cation are considerably increased in the synergy of multiple groups, with existing skill
Anion-nonionic surfactant in art is compared, and the surfactant salt resistance ability that the present invention is adopted is higher, can be used for height
The oil reservoir displacement of reservoir oil of salinity, with very high theory significance, and is with a wide range of applications and practical significance.
Surfactant of the present invention in 85 DEG C of Zhongyuan Oil Field Pu Chengxi Districts formation temperature, salinity 80000-300000mg/L,
Ca2+、Mg2+Concentration is still can to form 10 with the block dewatered oil under conditions of 1000-6000mg/L-3MN/m quantity
The ultralow interfacial tension of level, so as to drive crude oil, improves recovery ratio more than 10%, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 1.5mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(3) ether.
B) step a) gained NPE (3) is added to equipped with agitating device, condensation reflux unit and is divided
In the reactor of water installations, 250 milliliters of benzene and 40 grams of NaOH are added, alkalized 2 hours at 60 DEG C, added
0.61mol 3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, concentration is added dropwise is
The pH of system is transferred to 2 by the hydrochloric acid of 6M, is extracted with ethyl acetate, and oil phase is evaporated off after solvent, with sodium hydroxide solution
With then in volume ratio acetone:Ethanol:Water is 2:1:3- (NPEs are recrystallized to give in 1 mixed solvent
(3)) -2- hydroxy-propanesulfonic acids salt (0.39mol).
C) 3- (NPE (3)) -2- hydroxy-propanesulfonic acid salt for synthesizing step b), is added to equipped with condensation
In the reactor of device, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water are added, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized,
Purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 0.39mol oxirane, control pressure
Power≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 3- (nonyls after cooling
Base phenol polyethenoxy ether (3)) -2- (APEO (1)) propane sulfonic acid salt (0.39mol).
D) 3- (NPE (3)) -2- (APEO (1)) the propane sulfonic acid salt for synthesizing step c)
(0.39mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.78mol) are risen, is alkalized 2 hours at 60 DEG C, add 0.47mol 3- chlorine-2-hydroxyl propane sulfonic acid
Sodium, at reflux, reacts 5 hours, and (hydroxypropyl sulfonic acid gathers to obtain 3- (NPE (3)) -2-
Oxygen vinethene (1)) propane sulfonic acid salt (0.35mol).
2. surfactant properties evaluation
Oil displacement agent is prepared:
The weight portion of above-mentioned surfactant 1 and Pu Chengxi Districts are injected into the transparent oil displacement agent use that the weight portion of water 500 is mixed to get
In interfacial tension evaluation and oil displacement experiment.Injection water in Pu Chengxi Districts used wherein in all embodiments of the invention and comparative example
Composition is shown in Table 1.Composition for ease of comparing oil displacement agent is listed in table 2.
A) interfacial tension evaluation
TX-500C rotating interfacial tensimeters are produced using Texas ,Usa university, at 85 DEG C, rotating speed is 4500 turns
/ point under the conditions of, the interfacial tension determined between the dewatered oil of above-mentioned oil displacement agent and the extraction of Pu Chengxi Districts the results are shown in Table 3.
B) oil displacement experiment evaluation
Imitate according to the composite oil-displacing system physical simulation flooding test in SY/T6424-2000 composite oil-displacing system performance test methods
Fruit is tested, and at 85 DEG C, length is 30cm, and a diameter of 2.5cm, permeability is 1.5m2Rock core on be simulated drive
Oil experiment.First water drive is carried out to aqueous 98% with Pu Chengxi Districts injection water, after water drive terminates, metaideophone 0.3pv (rock core holes
Volume) above-mentioned oil displacement agent, then to aqueous 98%, raising oil recovery factor the results are shown in Table 4 to water drive.
【Embodiment 2】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 0.5mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 130 grams of Nonyl phenos (1) after cooling
Ether.
B) step a) gained 0.5mol NPEs (1) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.6mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (1)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (NPE (1)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 1.5 grams of water, side are added
When logical nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, is vacuumized de-
Water 1 hour, is purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.52mol epoxy second
Alkane, control pressure≤0.40MPa reactions；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (1)) -2- (APEO (4)) propane sulfonic acid salt 0.37mol.
D) 3- (NPE (1)) -2- (APEO (4)) the propane sulfonic acid salt for synthesizing step c)
(0.37mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.74mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.45mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (1)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (4)) propane sulfonic acid salt (0.35mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 3】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 1.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(2) ether.
B) step a) gained 0.49mol NPEs (2) is added to equipped with agitating device, is condensed back
In the reactor of stream device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, alkalization 2 is little at 60 DEG C
When, 0.59mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, react 8 hours.After reaction terminates, drop
Plus the pH of system is transferred to 2 by concentration for the hydrochloric acid of 6M, is extracted with ethyl acetate, oil phase is evaporated off after solvent, uses hydrogen-oxygen
Change sodium solution neutralization, then in volume ratio acetone:Ethanol:Water is 2:1:3- (nonyl phenols are recrystallized to give in 1 mixed solvent
APEO (2)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (NPE (2)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 1.5 grams of water, side are added
When logical nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, is vacuumized de-
Water 1 hour, is purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 0.76mol epoxy second
Alkane, control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration after cooling,
Obtain 3- (NPE (2)) -2- (APEO (2)) propane sulfonic acid salt 0.36mol.
D) 3- (NPE (2)) -2- (APEO (2)) the propane sulfonic acid salt for synthesizing step c)
(0.36mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.72mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.42mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (2)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (2)) propane sulfonic acid salt (0.32mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 4】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 2.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(4) ether.
B) step a) gained 0.49mol NPEs (4) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (4)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (NPE (4)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 0.76mol oxirane,
Control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (4)) -2- (APEO (2)) propane sulfonic acid salt 0.37mol.
D) 3- (NPE (2)) -2- (APEO (2)) the propane sulfonic acid salt for synthesizing step c)
(0.36mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.72mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.42mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (2)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (2)) propane sulfonic acid salt (0.34mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 5】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 3.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(6) ether.
B) step a) gained 0.49mol NPEs (6) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 500 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol.
C) step b) is synthesized into 3- (NPE (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.18mol oxirane,
Control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (6)) -2- (APEO (3)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (6)) -2- (APEO (3)) the propane sulfonic acid salt for synthesizing step c)
(0.38mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.76mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.44mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (6)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (3)) propane sulfonic acid salt (0.33mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 6】
1. prepared by surfactant
The surfactant synthesized using embodiment 5, except that compound concentration.
2. oil displacement agent performance evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 7】
1. prepared by surfactant
The surfactant synthesized using embodiment 5, except that compound concentration.
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 8】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 4.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(8) ether.
B) step a) gained 0.49mol NPEs (8) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (8)) -2- hydroxy-propanesulfonic acid salt 0.39mol.
C) step b) is synthesized into 3- (NPE (8)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 15 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.17mol oxirane,
Control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (8)) -2- (APEO (3)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (8)) -2- (APEO (3)) the propane sulfonic acid salt for synthesizing step c)
(0.38mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.76mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.44mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (8)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (3)) propane sulfonic acid salt (0.36mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 9】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 2.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(4) ether.
B) step a) gained 0.49mol NPEs (4) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (4)) -2- hydroxy-propanesulfonic acid salt 0.39mol.
C) step b) is synthesized into 3- (NPE (4)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 0.39mol oxirane,
Control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (4)) -2- (APEO (1)) propane sulfonic acid salt 0.39mol.
D) 3- (NPE (4)) -2- (APEO (1)) the propane sulfonic acid salt for synthesizing step c)
(0.39mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.78mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.48mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (4)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (1)) propane sulfonic acid salt (0.35mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 10】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 6.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.5mol Nonyl phenos after cooling
(12) ether.
B) step a) gained 0.5mol NPEs (12) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 400 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.6mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (12)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (NPE (12)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 3.8mol oxirane, control
Pressing pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
3- (NPE (12)) -2- (APEO (10)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (12)) -2- (APEO (10)) the propane sulfonic acid salt for synthesizing step c)
(0.38mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.76mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.45mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (NPE (12)) -2- (hydroxypropyl sulfonic acid polyoxies
Vinethene (10)) propane sulfonic acid salt (0.35mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 11】
1. prepared by surfactant
A) 0.5mol octyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 1.5mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol octyl phenol polyoxyethylene after cooling
(3) ether.
B) step a) gained 0.49mol OPEOs (3) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 300 milliliters of benzene and 38 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (octyl phenol polyoxies are recrystallized to give in 1 mixed solvent
Vinethene (3)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (NPE (3)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 15 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.2mol oxirane, control
Pressing pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
3- (OPEO (3)) -2- (APEO (3)) propane sulfonic acid salt 0.38mol.
D) 3- (OPEO (3)) -2- (APEO (3)) the propane sulfonic acid salt for synthesizing step c)
(0.38mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.76mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.44mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (OPEO (3)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (3)) propane sulfonic acid salt (0.34mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 12】
1. prepared by surfactant
A) 0.5mol gram of octyl phenol and 1.5 is added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 4.2mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.5mol octyl phenol polyoxyethylene after cooling
(8) ether.
B) step a) gained 0.5mol OPEOs (8) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 250 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.6mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (octyl phenol polyoxies are recrystallized to give in 1 mixed solvent
Vinethene (8)) -2- hydroxy-propanesulfonic acid salt 0.38mol.
C) step b) is synthesized into 3- (OPEO (8)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 15 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 2.0mol oxirane, control
Pressing pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
3- (OPEO (8)) -2- (APEO (5)) propane sulfonic acid salt 0.38mol.
D) 3- (OPEO (8)) -2- (APEO (5)) the propane sulfonic acid salt for synthesizing step c)
(0.38mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.76mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.45mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (OPEO (8)) -2- (hydroxypropyl sulfonic acid polyoxy second
Alkene ether (5)) propane sulfonic acid salt (0.35mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 13】
1. prepared by surfactant
A) 0.5mol amylic phenols and 1 gram are added in the reactor equipped with condensing unit, agitating device and gas distributor
NaOH and 10 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then 4 times are purged with the air in removing system with nitrogen, then by body
It is that reaction temperature is adjusted to 150 DEG C and is slowly passed through 2.6mol oxirane, it is anti-that control pressure≤0.40MPa carries out ethoxylation
Should；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.5mol amyl group phenol polyethenoxies (5) after cooling
Ether.
B) step a) gained 0.5mol amyl group phenol polyethenoxy (5) ethers are added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 500 milliliters of benzene solvents and 40 grams of NaOH are added, alkalize 2 at 60 DEG C
Hour, 0.6mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, react 8 hours.After reaction terminates,
Excessive watery hydrochloric acid is added dropwise the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses hydroxide
Sodium solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:0.36mol 3- (penta are recrystallized to give in 1 mixed solvent
Base phenol polyethenoxy (5) ether) -2- hydroxy-propanesulfonic acid salt.
C) 3- (amyl group phenol polyethenoxy (5) the ether) -2- hydroxy-propanesulfonic acid salt 0.35mol for synthesizing step b), are added to
In reactor equipped with condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 15 grams of water, side are added
When logical nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, is vacuumized de-
Water 1 hour, is purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 0.72mol epoxy second
Alkane, control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration after cooling,
Obtain 3- (amyl group phenol polyethenoxy (5) ether) -2- (polyoxyethylene (2) ether) propane sulfonic acid salt 0.35mol.
D) 3- (amyl group phenol polyethenoxy (5) ether) -2- (polyoxyethylene (2) ether) the propane sulfonic acid salt for synthesizing step c)
(0.35mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.70mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.40mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, obtain 3- (amyl group phenol polyethenoxy (5) ether) -2- (hydroxypropyl sulfonic acid polyoxies
Ethene (2) ether) propane sulfonic acid salt (0.31mol).
2. surfactant properties evaluation
In addition to oil displacement agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Embodiment 14】
1. prepared by surfactant
A) to equipped with condensing unit, agitating device and gas distributor reactor in add 0.5mol dodecylphenols and
1.5 grams of NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 1.1mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.5mol dodecylphenol polyoxies after cooling
Ethene (2) ether.
B) step a) gained 0.5mol dodecyl phenol polyethenoxy (2) ethers are added to equipped with agitating device, condensation
In the reactor of reflux and division box, 400 milliliters of benzene solvents and 30 grams of NaOH, the alkali at 60 DEG C are added
Change 2 hours, add 0.6mol 3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.Reaction terminates
Afterwards, concentration is added dropwise and the pH of system is transferred to into 2 for the hydrochloric acid of 6M, be extracted with ethyl acetate, oil phase is evaporated off after solvent,
Neutralized with sodium hydroxide solution, then in volume ratio acetone:Ethanol:Water is 2:1:3- is recrystallized to give in 1 mixed solvent
(dodecyl phenol polyethenoxy (2) ether) -2- hydroxy-propanesulfonic acid salt 0.36mol.
C) step b) is synthesized into 3- (dodecyl phenol polyethenoxy (2) ether) -2- hydroxypropionate sodium 0.36mol, is added
To in the reactor equipped with condensing unit, agitating device and gas distributor, 1.5 grams of NaOH and 15 grams of water are added,
When being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, is vacuumized
Dehydration 1 hour, is purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.5mol epoxy second
Alkane, control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration after cooling,
Obtain 3- (dodecyl phenol polyethenoxy (2) ether) -2- (polyoxyethylene (4) ether) sulfonate 0.36mol.
D) 3- (dodecyl phenol polyethenoxy (2) ether) -2- (polyoxyethylene (4) ether) sulfonate for synthesizing step c)
(0.36mol) in being added to the reactor equipped with agitating device, condensation reflux unit and division box, 200 millis are added
Benzene and NaOH (0.72mol) are risen, are alkalized 2 hours at 60 DEG C, add 0.42mol 3- chlorine-2-hydroxyl propanesulfonates,
At reflux, react 5 hours, (hydroxypropyl sulfonic acid gathers to obtain 3- (dodecyl phenol polyethenoxy (2) ether) -2-
Oxygen ethene (4) ether) sulfonate (0.33mol).
2. surfactant properties evaluation
Method of evaluating performance is with embodiment 1.Composition for ease of comparing oil displacement agent is listed in table 2, and evaluation result is listed in into table
3 and table 4.
【Embodiment 15】
1. prepared by surfactant
A) to equipped with condensing unit, agitating device and gas distributor reactor in add 0.5mol cetyls phenol and
2 grams of NaOH and 20 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 2.5mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol cetyl phenol polyoxies after cooling
Ethene (5) ether.
B) step a) gained 0.49mol cetyl phenol polyethenoxy (5) ethers are added to equipped with agitating device, condensation
In the reactor of reflux and division box, 400 milliliters of benzene solvents and 26 grams of NaOH, the alkali at 60 DEG C are added
Change 2 hours, add 0.58mol 3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.Reaction terminates
Afterwards, concentration is added dropwise and the pH of system is transferred to into 2 for the hydrochloric acid of 6M, be extracted with ethyl acetate, oil phase is evaporated off after solvent,
Neutralized with sodium hydroxide solution, then in volume ratio acetone:Ethanol:Water is 2:1:3- is recrystallized to give in 1 mixed solvent
(cetyl phenol polyethenoxy (5) ether) -2- hydroxy-propanesulfonic acid salt 0.36mol.
C) step b) is synthesized into 3- (cetyl phenol polyethenoxy (5) ether) -2- hydroxy-propanesulfonic acid salt 0.36mol, is added
To in the reactor equipped with condensing unit, agitating device and gas distributor, 1 gram of NaOH and 10 grams of water are added,
When being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, is vacuumized
Dehydration 1 hour, is purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.8mol epoxy second
Alkane, control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration after cooling,
Obtain 3- (cetyl phenol polyethenoxy (5) ether) -2- (polyoxyethylene (5) ether) propane sulfonic acid salt 0.35mol.
D) 3- (cetyl phenol polyethenoxy (5) ether) -2- (polyoxyethylene (5) ether) the third sulphur for synthesizing step c)
Hydrochlorate (0.35mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, adds 200
Milliliter benzene and NaOH (0.70mol), alkalize 2 hours at 60 DEG C, add 0.40mol 3- chlorine-2-hydroxyl propane sulfonic acid
Sodium, at reflux, reacts 5 hours, obtains 3- (cetyl phenol polyethenoxy (5) ether) -2- (hydroxypropyls
Sulfonic polyethenoxy (5) ether) propane sulfonic acid salt (0.31mol).
2. surfactant properties evaluation
Oil displacement agent is prepared:
3- (cetyl phenol polyethenoxy (5) the ether) -2- (polyoxyethylene (5) ether) third that above-mentioned steps c) is synthesized
The weight portion of sulfonate 1, the weight portion of monoethanolamine 0.5 and Pu Chengxi Districts injection water 500 weight portion is mixed 1 hour, is obtained
To a kind of oil displacement agent of homogeneous transparent.Other performance evaluation method is with embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in into table 3 and table 4.
【Comparative example 1】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 4.5mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction 4 hours；After reaction terminates, system is purged with nitrogen, neutralization, dehydration after cooling obtain 0.49mol nonyl phenols and gather
Oxygen ethene (6) polyoxyethylene (3) ether.
B) step a) gained 0.49mol Nonyl phenos (9) ethers are added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 500 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Ethene (9) ether) -2- hydroxy-propanesulfonic acid salt 0.38mol, structure is as follows：
2. surfactant properties evaluation
By 3- (Nonyl pheno (9) ether) weight portions of -2- hydroxy-propanesulfonic acids salt 1 of above-mentioned synthesis and Pu Chengxi Districts
Injection water 500 weight portion is mixed 1 hour, obtains displacement of reservoir oil agent solution.
A) interfacial tension evaluation
TX-500C rotating interfacial tensimeters are produced using Texas ,Usa university, at 85 DEG C, rotating speed is 4500 turns
/ point under the conditions of, the interfacial tension result determined between above-mentioned oil displacement agent and Pu Chengxi Districts injection water and the dewatered oil of extraction is shown in
Table 5.
B) oil displacement experiment evaluation
Imitate according to the composite oil-displacing system physical simulation flooding test in SY/T6424-2000 composite oil-displacing system performance test methods
Fruit is tested, and at 85 DEG C, length is 30cm, and a diameter of 2.5cm, permeability is 1.5m2Rock core on be simulated drive
Oil experiment.First water drive is carried out to aqueous 98% with Pu Chengxi Districts injection water, after water drive terminates, metaideophone 0.3pv (rock core holes
Volume) above-mentioned oil displacement agent, then to aqueous 98%, raising oil recovery factor the results are shown in Table 5 to water drive.
【Comparative example 2】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added in the reactor equipped with condensing unit, agitating device and gas distributor
Gram NaOH and 15 grams of water, when being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Open vacuum system,
At a temperature of 90 DEG C, dehydration 1 hour is vacuumized, then purge 4 times with the air in removing system with nitrogen, then will
System reaction temperature is adjusted to 150 DEG C and is slowly passed through 3.0mol oxirane, and control pressure≤0.40MPa carries out ethoxylation
Reaction；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain 0.49mol Nonyl phenos after cooling
(6) ether.
B) step a) gained 0.49mol NPEs (6) is added to equipped with agitating device, condensing reflux
In the reactor of device and division box, 500 milliliters of benzene and 40 grams of NaOH are added, are alkalized 2 hours at 60 DEG C,
0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, is reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend the hydrochloric acid for 6M and the pH of system is transferred to into 2, be extracted with ethyl acetate, oil phase is evaporated off after solvent, uses NaOH
Solution is neutralized, then in volume ratio acetone:Ethanol:Water is 2:1:3- (polyoxyethylene nonyl phenyls are recrystallized to give in 1 mixed solvent
Vinethene (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol.
C) step b) is synthesized into 3- (NPE (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In having the reactor of condensing unit, agitating device and gas distributor, 2 grams of NaOH and 20 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 is vacuumized
Hour, purged 4 times with nitrogen, then system reaction temperature is adjusted to into 150 DEG C and is slowly passed through 1.18mol oxirane,
Control pressure≤0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralization, dehydration, obtain after cooling
To 3- (NPE (6)) -2- (APEO (3)) propane sulfonic acid salt 0.38mol, structure is as follows：
2. surfactant properties evaluation
The weight portion of above-mentioned surfactant 1 and Pu Chengxi Districts injection water 500 weight portion are mixed 1 hour, one is obtained
Plant the oil displacement agent of homogeneous transparent.Result is listed in table 5 by other with comparative example 1 for ease of comparing.
Water is injected in the Zhongyuan Oil Field Pu Chengxi Districts of table 1
| Project | Na++K+ | Mg2+ | Ca2+ | Cl- | SO4 2- | HCO3 - | TDS |
| mg/L | 85066 | 367 | 3840 | 138006 | 1089 | 282 | 228650 |
The embodiment 1-15 oil displacement agent of table 2 is constituted
The embodiment 1-15 oil displacement agent interfacial tension performance of table 3
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0065 |
| 2 | 0.0074 |
| 3 | 0.0026 |
| 4 | 0.0018 |
| 5 | 0.0012 |
| 6 | 0.0002 |
| 7 | 0.0065 |
| 8 | 0.0015 |
| 9 | 0.0058 |
| 10 | 0.0073 |
| 11 | 0.0040 |
| 12 | 0.0041 |
| 13 | 0.0235 |
| 14 | 0.0082 |
| 15 | 0.0043 |
The embodiment 1-15 oil displacement experiment result of table 4
| Embodiment | Improve recovery ratio % |
| 1 | 4.9 |
| 2 | 5.2 |
| 3 | 7.1 |
| 4 | 10.1 |
| 5 | 9.8 |
| 6 | 11.5 |
| 7 | 4.9 |
| 8 | 7.8 |
| 9 | 6.3 |
| 10 | 5.3 |
| 11 | 7.1 |
| 12 | 6.1 |
| 13 | 4.0 |
| 14 | 4.2 |
| 15 | 5.5 |
The comparative example 1-2 the performance test results of table 5
| Comparative example | Interfacial tension (mN/m) | Improve recovery ratio % |
| 1 | 0.021 | 4.2 |
| 2 | 0.067 | 3.9 |
Claims (10)
1. salt tolerant oil displacement surfactant, its entitled 3- (alkyl phenol polyethenoxy ether) -2- (hydroxypropyl sulfonic acid polyoxy
Vinethene) propane sulfonic acid salt, shown in structure such as formula (I)：
Wherein M1And M2Be independently selected from in alkali metal, alkaline-earth metal any one, work as M1For alkali metal when n1For 1, when
M1For alkaline-earth metal when n1For 0.5, work as M2For alkali metal when n2For 1, work as M2For alkaline-earth metal when n2For 0.5, R
For C4～C20Alkyl, x=1～20, y=1～10.
2. salt tolerant oil displacement surfactant according to claim 1, it is characterised in that x=2～8, y=2～8.
3. salt tolerant oil displacement surfactant according to claim 2, it is characterised in that the alkyl is C7～C10Alkane
Base.
4. the preparation method of the salt tolerant oil displacement surfactant described in claim 1, comprises the following steps：
A) under base catalyst effect, alkyl phenol obtains alkyl phenol polyethenoxy ether with aequum reacting ethylene oxide；
B) step a) gained alkyl phenol polyethenoxy ethers are dissolved into into C6～C8In aromatic hydrocarbons, add alkali metal hydroxide or
At least one alkali in alkaline earth metal hydroxide, alkalizes 0.5～3 hour at 30～60 DEG C, adds 3- chlorine-2-hydroxyls
The alkali metal salt of propane sulfonic acid, the lower reaction of stirring obtains 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt；
C) by step b) gained 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt, in base catalyst effect
Under, obtain the 3- (alkyl phenol polyethenoxy ether) -2- (APEO) propane sulfonic acid with aequum reacting ethylene oxide
Salt；
D) by step c) gained 3- (alkyl phenol polyethenoxy ether) -2- (APEO) propane sulfonic acid salt, it is dissolved into
C6～C8In aromatic hydrocarbons, alkali metal hydroxide or at least one alkali in alkaline earth metal hydroxide are added, at 30～60 DEG C
Lower alkalization 0.5～3 hour, adds the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid, the lower reaction of stirring to obtain 3- (alkyl phenol
APEO) -2- (hydroxypropyl sulfonic acid APEO) propane sulfonic acid salt.
5. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/
Or the step c) base catalysts are alkali metal hydroxide or at least one in alkaline-earth metal.
6. the preparation method of salt tolerant oil displacement surfactant according to claim 4, is characterized in that step b) is described
Alkyl phenol polyethenoxy ether is 1 with the mol ratio of 3- chlorine-2-hydroxyl propane sulfonic acid alkali metal salts:(1～2), the reaction time
For 6～10 hours.
7. the preparation method of salt tolerant oil displacement surfactant according to claim 5, is characterized in that step a) and step
Rapid c) described base catalyst is NaOH or at least one in potassium hydroxide.
8. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/
Or the step c) reaction temperatures are 120～140 DEG C, the reaction time is 6～8 hours.
9. application of the surfactant described in claim 1 in oil recovery factor is improved.
10. application according to claim 9, it is characterized in that application process be by terms of parts by weight including the table
The oil displacement agent injection oil bearing bed of 100～2000 parts of 1 part of face activating agent and water.
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| CN111087601A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Surfactant and composition for oil extraction and preparation method thereof |
| CN111088013A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
| CN111088014A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
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| CN111087601A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Surfactant and composition for oil extraction and preparation method thereof |
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| CN111088014B (en) * | 2018-10-23 | 2022-02-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
| CN111088013B (en) * | 2018-10-23 | 2022-07-12 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
| CN111087601B (en) * | 2018-10-23 | 2022-08-12 | 中国石油化工股份有限公司 | Surfactant and composition for oil extraction and preparation method thereof |
| CN113896881A (en) * | 2020-07-06 | 2022-01-07 | 中国石油化工股份有限公司 | Alkyl naphthylamine polyether naphthalene sulfonate surfactant and preparation method and application thereof |
| CN115069199A (en) * | 2022-07-14 | 2022-09-20 | 山东大明精细化工有限公司 | Preparation process of sodium alkyl polyoxyethylene ether sulfonate |
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