WO2022099826A1 - Gemini polyoxyethylene ether succinate surfactant for oil displacement and preparation method therefor - Google Patents
Gemini polyoxyethylene ether succinate surfactant for oil displacement and preparation method therefor Download PDFInfo
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- WO2022099826A1 WO2022099826A1 PCT/CN2020/133229 CN2020133229W WO2022099826A1 WO 2022099826 A1 WO2022099826 A1 WO 2022099826A1 CN 2020133229 W CN2020133229 W CN 2020133229W WO 2022099826 A1 WO2022099826 A1 WO 2022099826A1
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- WIPO (PCT)
- Prior art keywords
- gemini
- polyoxyethylene ether
- surfactant
- preparation
- oil displacement
- Prior art date
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- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 79
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 78
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 44
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000011549 displacement method Methods 0.000 title 1
- 238000006073 displacement reaction Methods 0.000 claims abstract description 21
- -1 polyoxyethylene sulfosuccinate Polymers 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 150000007942 carboxylates Chemical class 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 10
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004945 emulsification Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000009671 shengli Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/20—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by addition of sulfurous acid or salts thereof to compounds having carbon-to-carbon multiple bonds
-
- 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
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Definitions
- the invention relates to a Gemini polyoxyethylene ether succinate surfactant for oil displacement and a preparation method thereof.
- the chemical flooding in the tertiary oil recovery technology uses chemical substances to improve the performance between oil, gas, water and rock. Generally, the recovery factor can be increased by about 20% on the basis of water flooding.
- chemical flooding in various oilfields in my country is mainly binary or ternary composite flooding technology, especially surfactant flooding based on the ultra-low interfacial tension mechanism. This technology has good universality and economy, and compared with other technologies obvious advantage.
- surfactants suitable for compound flooding such as petroleum sulfonates, heavy alkyl benzene sulfonates, natural carboxylates and petroleum carboxylates, will cause salting out and hydrolysis problems, resulting in unsatisfactory temperature and salt resistance and interfacial activity.
- a surfactant cannot meet the requirements of emulsification and viscosity reduction, wetting and washing oil, and low interfacial tension. Harsh technical indicators are generally improved by the use of surfactants. As described in the patent CN107365575A, it can be applied to oil reservoirs with a viscosity up to 200 mPa ⁇ s through technical improvement, and the recovery factor is increased to more than 17.6%, but it is necessary to use alkyl alcohol polyoxyethylene ether or its derivatives and ester compounds, Wetting agents are used in combination.
- the invention provides a Gemini polyoxyethylene ether succinate surfactant for oil displacement and a preparation method thereof.
- the technical problem is solved by synthesizing Gemini alkylphenol polyoxyethylene ether through condensation, maleic anhydride carboxylation and addition sulfonation. Sulfosuccinate, the structure of the existing Gemini alkylphenol polyoxyethylene ether has been optimized.
- the alkylbenzene structure is similar to the aromatic structure of crude oil, and it has both the emulsification function of phenol polyoxyethylene ether for crude oil.
- the introduction of the twin structure strengthens this function, and at the same time, the succinic acid structure is introduced into the functional structure of the molecule, which combines the mildness of sodium carboxylate and the resistance to hard water, salt and temperature of sodium sulfonate, improving the wetting performance at the same time. , effectively overcome the problem of chromatographic separation of compounding, and it also has good effect when used alone, and it is easy to use and does not need compounding.
- the present invention adopts the following technical solutions:
- a Gemini polyoxyethylene ether succinate surfactant for oil displacement is Gemini alkylphenol polyoxyethylene sulfosuccinate, and its general molecular formula is:
- M is a metal ion
- R is an alkyl group or an isomeric alkyl group with 1-20 carbon atoms
- n is any integer selected from 3-9.
- the metal ion M is one or more of sodium ion, potassium ion and lithium ion.
- a preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement The alkylphenol polyoxyethylene ether and paraformaldehyde are mixed, vacuumed to -0.06Mpa ⁇ -0.08Mpa, filled with nitrogen, and heated.
- the molar ratio of the alkylphenol polyoxyethylene ether to the paraformaldehyde is 2:1.
- the amount of maleic anhydride species is 1-1.4 times the amount of alkylphenol polyoxyethylene ether monomer species.
- the catalyst includes one or more of sodium nitrate, potassium nitrate and p-toluenesulfonic acid, and the dosage is 0.1-0.5% of the total mass of the reactants.
- the sulfonating agent includes one or more of sulfur trioxide solution, sodium bisulfite and potassium bisulfite, and the dosage of the sulfonating agent is 1.1-1.8 times of the mole number of alkylphenol polyoxyethylene ether.
- the solvent includes an alcohol with a carbon number of 1-5 or a solution that is miscible with water in any ratio.
- Described alkali solution is one or more in sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution and potassium bicarbonate aqueous solution.
- the concentration of the alkaline solution is 1% to 30%.
- the process principle of the present invention for preparing the Gemini alkylphenol polyoxyethylene ether sulfosuccinate surfactant is:
- the preparation method meets the requirements of atomic economy, no waste water, waste gas or waste residue is produced, and the solvent can be recycled and reused.
- the product yield of the preparation method by optimizing the process parameters is greater than 90%, and the residual unreacted reactants and salts are opposite to the product. The performance impact is small.
- the above-mentioned Gemini alkylphenol polyoxyethylene ether sulfosuccinate surfactant can be prepared quickly and efficiently.
- the present application synthesizes Gemini alkylphenol polyoxyethylene ether sulfosuccinate by condensation connection, maleic anhydride carboxylation, addition sulfonation, and structural optimization is carried out to the existing Gemini alkylphenol polyoxyethylene ether,
- the alkylbenzene structure and the aromatic structure of crude oil are similar and compatible, which not only has the emulsification function of phenol polyoxyethylene ether to crude oil, but the introduction of the gemini structure also strengthens this function, and at the same time, the succinic acid structure is introduced into the functional structure of the molecule.
- has the mildness of sodium carboxylate and the resistance to hard water, salt and temperature of sodium sulfonate improves the wetting performance, and effectively overcomes the problem of chromatographic separation of the compound. No recombination is required.
- the application can obtain Gemini polyoxyethylene ether succinate with higher yield through the control of the reaction temperature, so as to ensure the application effect of the application.
- a Gemini polyoxyethylene ether succinate surfactant for oil displacement is Gemini pentadecylphenol polyoxyethylene ether 9 sulfosuccinate;
- Step 1 Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9: the pentadecylphenol polyoxyethylene ether 9 is charged on a basis of 0.5mol, and 0.25mol of paraformaldehyde is added to a 500ml there-necked bottle and mixed, pumped. After vacuuming to -0.07MPa, nitrogen was charged to a pressure of 0.1MPa, and the reaction was carried out at a set temperature of 120° C. for 2 hours to obtain Gemini pentadecylphenol polyoxyethylene ether 9.
- Step 3 Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9 sulfosuccinate: the pentadecylphenol polyoxyethylene ether 9 carboxylate synthesized by the above-mentioned optimal process is fed according to 0.2 mol, and added. in a three-necked flask. Weigh 0.48 mol of sodium bisulfite, that is, the mass ratio of Gemini pentadecylphenol polyoxyethylene ether 9 carboxylate to sodium bisulfite is 1:2.4.
- the product prepared by the above method was tested in a high temperature, high salinity and low permeability reservoir in Shengli Oilfield for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension, and oil washing ability.
- the salinity of the sample is 35820 mg/L
- the Ca 2+ and Mg 2+ concentrations are 2230 mg/L
- the formation temperature is 90 °C
- the tension instrument is a TX500C transfer drop interfacial tension meter.
- a Gemini polyoxyethylene ether succinate surfactant for oil displacement is Gemini nonylphenol polyoxyethylene ether 4 sulfosuccinate;
- Step 1 the synthesis of Gemini nonylphenol polyoxyethylene ether 4: the nonylphenol polyoxyethylene ether 4 is charged on the basis of 0.5mol, and 0.25mol of paraformaldehyde is added to a 500ml there-necked bottle and mixed, and vacuumed to -0.07 After MPa, nitrogen was charged to a pressure of 0.1 MPa, and the reaction was carried out at a set temperature of 120° C. for 2 h to obtain Gemini nonylphenol polyoxyethylene ether 4.
- Step 3 Synthesis of Gemini nonylphenol polyoxyethylene ether 4 sulfosuccinate: The nonylphenol polyoxyethylene ether 4 carboxylate synthesized by the above-mentioned optimal process is charged according to 0.2 mol, and added to a three-necked flask. Weigh 0.48 mol of sodium bisulfite, that is, the mass ratio of Gemini nonylphenol polyoxyethylene ether 4 carboxylate to sodium bisulfite is 1:2.4.
- the products prepared by the above method were tested for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension and oil washing ability in a high-temperature and high-salinity reservoir in Zhongyuan Oilfield.
- the chemical degree is 158205 mg/L
- the Ca 2+ and Mg 2+ concentrations are 6230 mg/L
- the formation temperature is 87 °C
- the tension instrument is a TX500C transfer drop interfacial tension meter.
- a Gemini polyoxyethylene ether succinate surfactant for oil displacement is Gemini isomeric tenphenol polyoxyethylene ether 10 sulfosuccinate;
- Step 1 Synthesis of Gemini isomerized decahydrin polyoxyethylene ether 10: The isomerized decahydrin phenol ethoxylate 10 is charged on the basis of 0.5 mol, and 0.25 mol of paraformaldehyde is added to a 500ml three-necked bottle and mixed, pumped. The vacuum was reduced to -0.07MPa and then filled with nitrogen to a pressure of 0.1MPa, and the reaction was carried out at a set temperature of 120°C for 2 hours to obtain Gemini isomerized decahydrin polyoxyethylene ether 10.
- Step 3 Synthesis of Gemini isomerized decahydrin polyoxyethylene ether 10 sulfosuccinate: the isomerized decahydrin phenol ethoxylate 10 carboxylate synthesized by the above-mentioned optimal process was fed according to 0.2 mol, and added. in a three-necked flask. Weigh 0.48mol of sodium bisulfite, that is, the mass ratio of Gemini isomerized decahydrin polyoxyethylene ether 10 carboxylate to sodium bisulfite is 1:2.4.
- the products prepared by the above method were tested for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension, and oil washing ability in a high-temperature and high-salinity reservoir in Shengli Oilfield.
- the chemical degree is 35820 mg/L
- the Ca 2+ and Mg 2+ concentrations are 2230 mg/L
- the formation temperature is 82 °C
- the tension instrument is a TX500C transfer drop interfacial tension meter.
- Example 2 The above-mentioned products at different temperatures are continued to be completed according to the steps of Example 1 to synthesize the final product Gemini pentadecylphenol polyoxyethylene ether 9 sodium sulfosuccinate.
- the final product is formulated into a solution with an effective concentration of 0.3%, and is emulsified and reduced in viscosity (the mass ratio of crude oil and injected water is 7:3), oil-water interfacial tension, and oil washing capacity in a high-temperature, high-salinity and low-permeability oil reservoir in Shengli Oilfield.
- the salinity of the formation water sample is 35820mg/L
- the concentration of Ca 2+ and Mg 2+ is 2230mg/L
- the formation temperature is 90 °C
- the tension instrument is a TX500C transfer drop interfacial tension meter.
- Comparative Example 2 The product prepared by the method of Example 1 and lauryl alcohol polyoxyethylene ether 10 (here referred to as comparative example 1), lauryl alcohol polyoxyethylene ether 10 (30%), methyl myristate (2%) and wetting agent (0.5%) to prepare oil displacement agent (herein referred to as Comparative Example 2) for comparison, in a high temperature, high salinity and low permeability oil reservoir in Shengli Oilfield, emulsification and viscosity reduction (crude oil and The mass ratio of oil-displacing agent is 7:3), oil-water interfacial tension, and oil-washing ability detection.
- the salinity of the formation water sample is 35820mg/L, the concentration of Ca 2+ and Mg 2+ is 2230mg/L, and the formation temperature is 90 °C , the tension instrument is TX500C transfer drop interfacial tension meter, and the effective product concentration in the experiment is 0.3%.
- Example 1 97.3 74.8 4.3 ⁇ 10-3 30
- Comparative Example 1 50.2 32.5 8 ⁇ 10-2 >3min
- Comparative Example 2 95.3 68.9 1.2 ⁇ 10-2 twenty one
- the present invention obtains a brand-new anionic non-gemini surfactant Gemini alkylphenol polyoxyethylene ether sulfosuccinic acid by synthesizing a series of anionic-nonionic surfactants. And find a process route, so that it has the advantages of fast, high efficiency, high yield, environmental protection and safety in preparation, and the selection of process meets the requirements of green chemical industry and clean production, does not produce by-products or waste, and achieves "zero discharge of waste". ".
- Gemini alkylphenol polyoxyethylene ether sulfosuccinic acid provided by the invention has a salt resistance of more than 200,000 mg/L, and calcium and magnesium resistance of more than 5,000 mg/L, and has a good prospect of popularization and application and good social and economic benefits.
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Abstract
The present invention relates to a Gemini polyoxyethylene ether succinate surfactant for oil displacement and a preparation method therefor. The present invention is characterized in that the surfactant is a Gemini alkylphenol polyoxyethylene sulfosuccinate. In the present application, a Gemini alkylphenol polyoxyethylene ether sulfosuccinate with salt resistance, temperature tolerance and a relatively high wettability is synthesized, and the Gemini alkylphenol polyoxyethylene ether sulfosuccinate is particularly suitable for high-temperature and high-salt oil reservoirs. The Gemini-alkylphenol-polyoxyethylene-ether-sulfosuccinate-type temperature-resistant salt-tolerant ultralow-interfacial-tension surfactant provided by the present application has good popularization and application prospects and good social and economic benefits.
Description
本发明涉及一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂及其制备方法。The invention relates to a Gemini polyoxyethylene ether succinate surfactant for oil displacement and a preparation method thereof.
三次采油技术中的化学驱是用化学物质来改善油、气、水及岩石间的性能，一般可在水驱的基础上将采收率再提高20％左右。目前我国各油田化学驱主要是二元或三元复合驱技术，尤其是基于超低界面张力机理的表面活性剂驱，该技术具有良好的普适性和经济性，与其他技术相比表现出明显的优势。然而适用于复合驱的表面活性剂如石油磺酸盐、重烷基苯磺酸盐、天然羧酸盐以及石油羧酸盐会产生盐析及水解问题导致耐温抗盐性能及界面活性无法满足要求，而烷氧基羧酸盐、磺酸盐耐温抗盐性能得到改善，界面性能不足，为此新的驱油用表面活性剂的研制日益迫切。近年，Gemini表面活性剂在亲水基部位或近亲水基部位将两个传统的表面活性剂通过分子键结合起来，具有超低界面张力、低临界胶束浓度、低Kraff点、良好的钙皂分散能力和乳化渗透性，是近年表面活性剂领域的研究热点。The chemical flooding in the tertiary oil recovery technology uses chemical substances to improve the performance between oil, gas, water and rock. Generally, the recovery factor can be increased by about 20% on the basis of water flooding. At present, chemical flooding in various oilfields in my country is mainly binary or ternary composite flooding technology, especially surfactant flooding based on the ultra-low interfacial tension mechanism. This technology has good universality and economy, and compared with other technologies obvious advantage. However, surfactants suitable for compound flooding, such as petroleum sulfonates, heavy alkyl benzene sulfonates, natural carboxylates and petroleum carboxylates, will cause salting out and hydrolysis problems, resulting in unsatisfactory temperature and salt resistance and interfacial activity. However, the temperature and salt resistance of alkoxy carboxylates and sulfonates are improved, and the interface properties are insufficient. Therefore, the development of new surfactants for oil displacement is increasingly urgent. In recent years, Gemini surfactants combine two traditional surfactants through molecular bonds at the hydrophilic site or near-hydrophilic site, with ultra-low interfacial tension, low critical micelle concentration, low Kraff point, and good calcium soap. Dispersing ability and emulsifying permeability are the research hotspots in the field of surfactants in recent years.
在Gemini表面活性剂分子结构中，由于两个非离子头基靠联接基团通过化学键连接，由此造成了两个表面活性剂单体离子相当紧密的连接。致使其碳氢链间更容易产生强相互作用，即加强了碳氢链间的疏水结合力。而且亲水基间的排斥倾向受制于化学键力而被大大削弱，这可能是双子表面活性剂与普通表面活性剂具有高表面活性的根本原因。常用的非离子表面活性剂烷基醇聚氧乙烯醚作为乳化剂因溶解性差、浊点低等问题，通常一种表面活性剂无法同时满足乳化降粘、润湿洗油、低界面张力等日益苛刻的技术指标，一般采取表面活性剂复配的使用加以改善。如专利CN107365575A中所述通过技术改进可应用于粘度高达200mPa·s的的油藏，采收率提高至17.6％以上，但是需要采用烷基醇聚氧乙烯醚或其衍生物与酯类化合物、润湿剂复配使用。In the molecular structure of Gemini surfactants, two nonionic head groups are connected by chemical bonds through linking groups, thus resulting in a relatively tight connection between the two surfactant monomer ions. As a result, strong interactions between the hydrocarbon chains are more likely to occur, that is, the hydrophobic binding force between the hydrocarbon chains is strengthened. Moreover, the repelling tendency between hydrophilic groups is greatly weakened by the chemical bond force, which may be the fundamental reason for the high surface activity of gemini surfactants and common surfactants. The commonly used nonionic surfactants, alkyl alcohol polyoxyethylene ethers, are used as emulsifiers due to poor solubility and low cloud point. Usually, a surfactant cannot meet the requirements of emulsification and viscosity reduction, wetting and washing oil, and low interfacial tension. Harsh technical indicators are generally improved by the use of surfactants. As described in the patent CN107365575A, it can be applied to oil reservoirs with a viscosity up to 200 mPa·s through technical improvement, and the recovery factor is increased to more than 17.6%, but it is necessary to use alkyl alcohol polyoxyethylene ether or its derivatives and ester compounds, Wetting agents are used in combination.
发明内容SUMMARY OF THE INVENTION
本发明提供一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂及其制备方法，解决技术问 题是通过缩合，马来酸酐羧化，加成磺化合成Gemini烷基酚聚氧乙烯醚磺基琥珀酸盐，对现有的Gemini烷基酚聚氧乙烯醚进行了结构优化，烷基苯结构和原油的芳烃结构相似相溶，既兼具了酚聚氧乙烯醚对原油的乳化功能，双子结构的引入又强化了这种功能，同时将琥珀酸结构引入分子的官能结构中，兼有羧酸钠的温和性和磺酸钠的抗硬水耐盐耐温性，提高润湿性能同时，有效克服复配的色谱分离问题，且单独使用也具有较好的效果，使用方便，无需复配。The invention provides a Gemini polyoxyethylene ether succinate surfactant for oil displacement and a preparation method thereof. The technical problem is solved by synthesizing Gemini alkylphenol polyoxyethylene ether through condensation, maleic anhydride carboxylation and addition sulfonation. Sulfosuccinate, the structure of the existing Gemini alkylphenol polyoxyethylene ether has been optimized. The alkylbenzene structure is similar to the aromatic structure of crude oil, and it has both the emulsification function of phenol polyoxyethylene ether for crude oil. , the introduction of the twin structure strengthens this function, and at the same time, the succinic acid structure is introduced into the functional structure of the molecule, which combines the mildness of sodium carboxylate and the resistance to hard water, salt and temperature of sodium sulfonate, improving the wetting performance at the same time. , effectively overcome the problem of chromatographic separation of compounding, and it also has good effect when used alone, and it is easy to use and does not need compounding.
为了解决上述技术问题，本发明采用以下技术方案：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，所述表面活性剂为Gemini烷基酚聚氧乙烯磺基琥珀酸盐，其分子通式为：A Gemini polyoxyethylene ether succinate surfactant for oil displacement, the surfactant is Gemini alkylphenol polyoxyethylene sulfosuccinate, and its general molecular formula is:
其中M为金属离子，R为碳原子数1-20的烷基或异构烷基，n为选自3-9中的任意一个整数。wherein M is a metal ion, R is an alkyl group or an isomeric alkyl group with 1-20 carbon atoms, and n is any integer selected from 3-9.
所述金属离子M是所述金属离子M是钠离子、钾离子和锂离子中的一种或几种。The metal ion M is one or more of sodium ion, potassium ion and lithium ion.
一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，将烷基酚聚氧乙烯醚和多聚甲醛混合，抽真空至-0.06Mpa～-0.08Mpa后充入氮气，加热至100℃～120℃，在压力为0.05～0.5Mpa条件下，搅拌2h；降温至70℃～100℃，加入马来酸酐，反应4～6h，用碱溶液中和至产物溶液pH＝7左右；加入含有催化剂和磺化剂的溶剂，设定转速为350r/min，在设定加热温度为70℃～100℃条件下搅拌8～10h，即得驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂。A preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement. The alkylphenol polyoxyethylene ether and paraformaldehyde are mixed, vacuumed to -0.06Mpa～-0.08Mpa, filled with nitrogen, and heated. To 100℃～120℃, under the condition of pressure of 0.05～0.5Mpa, stir for 2h; cool down to 70℃～100℃, add maleic anhydride, react for 4～6h, neutralize with alkali solution to pH=7 of the product solution ; Add the solvent containing the catalyst and sulfonating agent, set the rotating speed to 350r/min, and stir for 8 to 10 hours under the condition that the set heating temperature is 70°C to 100°C to obtain Gemini polyoxyethylene ether succinate for oil displacement. Surfactant.
所述烷基酚聚氧乙烯醚与多聚甲醛的摩尔比为2:1。The molar ratio of the alkylphenol polyoxyethylene ether to the paraformaldehyde is 2:1.
马来酸酐物质的量为烷基酚聚氧乙烯醚单体物质的量的1-1.4倍。The amount of maleic anhydride species is 1-1.4 times the amount of alkylphenol polyoxyethylene ether monomer species.
所述催化剂包括硝酸钠、硝酸钾和对甲苯磺酸中的一种或几种，用量为反应物总质量的0.1-0.5％。The catalyst includes one or more of sodium nitrate, potassium nitrate and p-toluenesulfonic acid, and the dosage is 0.1-0.5% of the total mass of the reactants.
所述磺化剂包括三氧化硫溶液、亚硫酸氢钠和亚硫酸氢钾中的一种或几种，磺化剂用量为烷基酚聚氧乙烯醚摩尔数的1.1-1.8倍。The sulfonating agent includes one or more of sulfur trioxide solution, sodium bisulfite and potassium bisulfite, and the dosage of the sulfonating agent is 1.1-1.8 times of the mole number of alkylphenol polyoxyethylene ether.
所述溶剂包括碳数为1-5的醇或其与水任意比互溶的溶液。The solvent includes an alcohol with a carbon number of 1-5 or a solution that is miscible with water in any ratio.
所述碱溶液是氢氧化钠水溶液、氢氧化钾水溶液、碳酸钠水溶液和碳酸氢钾水溶液中的一 种或几种。Described alkali solution is one or more in sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution and potassium bicarbonate aqueous solution.
所述碱溶液的浓度为1％～30％。The concentration of the alkaline solution is 1% to 30%.
本发明制备所述Gemini烷基酚聚氧乙烯醚磺基琥珀酸盐表面活性剂的的工艺原理为：The process principle of the present invention for preparing the Gemini alkylphenol polyoxyethylene ether sulfosuccinate surfactant is:
发明具有以下有益技术效果：The invention has the following beneficial technical effects:
1.制备方法符合原子经济性要求，无废水、废气或废渣产生，溶剂可回收再利用，通过优化工艺参数的制备方法的产物收率大于90％，且残余未反应的反应物与盐对产品性能影响较小。可以快速、高效地制备获得上述Gemini烷基酚聚氧乙烯醚磺基琥珀酸盐表面活性剂。1. The preparation method meets the requirements of atomic economy, no waste water, waste gas or waste residue is produced, and the solvent can be recycled and reused. The product yield of the preparation method by optimizing the process parameters is greater than 90%, and the residual unreacted reactants and salts are opposite to the product. The performance impact is small. The above-mentioned Gemini alkylphenol polyoxyethylene ether sulfosuccinate surfactant can be prepared quickly and efficiently.
2.本申请通过缩合连接，马来酸酐羧化，加成磺化合成Gemini烷基酚聚氧乙烯醚磺基琥珀酸盐，对现有的Gemini烷基酚聚氧乙烯醚进行了结构优化，烷基苯结构和原油的芳烃结构相似相溶，既兼具了酚聚氧乙烯醚对原油的乳化功能，双子结构的引入又强化了这种功能，同时将琥珀酸结构引入分子的官能结构中，兼有羧酸钠的温和性和磺酸钠的抗硬水耐盐耐温性，提高润湿性能同时，有效克服复配的色谱分离问题，且单独使用也具有较好的效果，使用方便，无需复配。2. The present application synthesizes Gemini alkylphenol polyoxyethylene ether sulfosuccinate by condensation connection, maleic anhydride carboxylation, addition sulfonation, and structural optimization is carried out to the existing Gemini alkylphenol polyoxyethylene ether, The alkylbenzene structure and the aromatic structure of crude oil are similar and compatible, which not only has the emulsification function of phenol polyoxyethylene ether to crude oil, but the introduction of the gemini structure also strengthens this function, and at the same time, the succinic acid structure is introduced into the functional structure of the molecule. , has the mildness of sodium carboxylate and the resistance to hard water, salt and temperature of sodium sulfonate, improves the wetting performance, and effectively overcomes the problem of chromatographic separation of the compound. No recombination is required.
3.本申请通过反应温度的控制，可以获得产率较高的Gemini聚氧乙烯醚琥珀酸盐，以保证本申请的使用效果。3. The application can obtain Gemini polyoxyethylene ether succinate with higher yield through the control of the reaction temperature, so as to ensure the application effect of the application.
下面结合具体实例进一步说明本发明。The present invention is further described below in conjunction with specific examples.
实施例1Example 1
一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，所述表面活性剂为Gemini十五烷基酚聚氧乙烯醚9磺基琥珀酸盐；A Gemini polyoxyethylene ether succinate surfactant for oil displacement, the surfactant is Gemini pentadecylphenol polyoxyethylene ether 9 sulfosuccinate;
步骤1、Gemini十五烷基酚聚氧乙烯醚9的合成：将十五烷基酚聚氧乙烯醚9按0.5mol为基准投料，和多聚甲醛0.25mol加入到500ml三口瓶中混合，抽真空至-0.07MPa后充入氮气至压力0.1MPa，设定温度120℃下反应2h，得到Gemini十五烷基酚聚氧乙烯醚9。Step 1. Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9: the pentadecylphenol polyoxyethylene ether 9 is charged on a basis of 0.5mol, and 0.25mol of paraformaldehyde is added to a 500ml there-necked bottle and mixed, pumped. After vacuuming to -0.07MPa, nitrogen was charged to a pressure of 0.1MPa, and the reaction was carried out at a set temperature of 120° C. for 2 hours to obtain Gemini pentadecylphenol polyoxyethylene ether 9.
步骤2、Gemini十五烷基酚聚氧乙烯醚9羧酸盐的合成：将0.2mol Gemini十五烷基酚聚氧乙烯醚9与0.42mol马来酸酐加入到三口烧瓶中，即Gemini十五烷基酚聚氧乙烯醚9与马来酸酐按物质的量比为1：2.1投料，设定温度为100℃，搅拌4h。停止反应，取样用NaOH标准溶液测量酸值，计算得转化率95.72％。加入浓度为20％的氢氧化钠溶液，将产物中和至pH＝7。Step 2. Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9 carboxylate: add 0.2mol of Gemini pentadecylphenol polyoxyethylene ether 9 and 0.42mol maleic anhydride into the three-necked flask, namely Gemini fifteen Alkylphenol polyoxyethylene ether 9 and maleic anhydride were charged in a material ratio of 1:2.1, the set temperature was 100°C, and the mixture was stirred for 4 hours. The reaction was stopped, the acid value was measured with NaOH standard solution by sampling, and the conversion rate was calculated to be 95.72%. The product was neutralized to pH=7 by adding 20% sodium hydroxide solution.
步骤3、Gemini十五烷基酚聚氧乙烯醚9磺基琥珀酸盐的合成：将上述最优工艺合成的十五烷基酚聚氧乙烯醚9羧酸盐按0.2mol为基准投料，加入三口烧瓶中。称取0.48mol亚硫酸氢钠，即Gemini十五烷基酚聚氧乙烯醚9羧酸盐与亚硫酸氢钠物质的量比为1：2.4。称取反应物总质量0.2％的硝酸钠，将催化剂硝酸钠与磺化剂亚硫酸氢钠溶于去离子水与正丁醇体积比1：1的醇水溶液中，制成浓度为20％的溶液。将含有催化剂与磺化剂的溶液加入到三口烧瓶中，设定温度为100℃，回流搅拌反应8小时。反应结束后用硫代硫酸钠标准液滴定产物中剩余的亚硫酸钠，计算测定转化率为96.3％。Step 3. Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9 sulfosuccinate: the pentadecylphenol polyoxyethylene ether 9 carboxylate synthesized by the above-mentioned optimal process is fed according to 0.2 mol, and added. in a three-necked flask. Weigh 0.48 mol of sodium bisulfite, that is, the mass ratio of Gemini pentadecylphenol polyoxyethylene ether 9 carboxylate to sodium bisulfite is 1:2.4. Weigh 0.2% sodium nitrate of the total mass of the reactants, dissolve the catalyst sodium nitrate and the sulfonating agent sodium bisulfite in an alcohol aqueous solution with a volume ratio of 1:1 of deionized water and n-butanol to prepare a 20% concentration of sodium nitrate. solution. The solution containing the catalyst and the sulfonating agent was added to a three-necked flask, the temperature was set to 100° C., and the reaction was stirred under reflux for 8 hours. After the reaction, the remaining sodium sulfite in the product was titrated with sodium thiosulfate standard titration, and the conversion rate was calculated and determined to be 96.3%.
采用上述方法制备得到的产品，在胜利油田某高温高矿化度低渗油藏进行乳化降粘(原油与注入水质量比为7:3)、油水界面张力、洗油能力检测，其中地层水样矿化度为35820mg/L，Ca
2+和Mg
2+浓度为2230mg/L，地层温度90℃，张力仪器为TX500C型转滴界面张力仪。
The product prepared by the above method was tested in a high temperature, high salinity and low permeability reservoir in Shengli Oilfield for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension, and oil washing ability. The salinity of the sample is 35820 mg/L, the Ca 2+ and Mg 2+ concentrations are 2230 mg/L, the formation temperature is 90 °C, and the tension instrument is a TX500C transfer drop interfacial tension meter.
| 有效产品浓度，％Effective Product Concentration, % | 乳化降粘，％Emulsified viscosity reduction, % | 洗油效率，％Oil washing efficiency, % | 界面张力，mN/mInterfacial tension, mN/m | 渗透性，spermeability, s |
| 0.10.1 | 96.196.1 | 61.261.2 | 6.1×10 -3 6.1× 10-3 | 5858 |
| 0.30.3 | 97.397.3 | 74.874.8 | 4.3×10 -3 4.3× 10-3 | 3030 |
| 0.60.6 | 98.998.9 | 80.680.6 | 2.1×10 -3 2.1× 10-3 | 66 |
实施例2Example 2
一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，所述表面活性剂为Gemini壬基酚聚氧乙烯醚4磺基琥珀酸盐；A Gemini polyoxyethylene ether succinate surfactant for oil displacement, the surfactant is Gemini nonylphenol polyoxyethylene ether 4 sulfosuccinate;
步骤1、Gemini壬基酚聚氧乙烯醚4的合成：将壬基酚聚氧乙烯醚4按0.5mol为基准投料，和多聚甲醛0.25mol加入到500ml三口瓶中混合，抽真空至-0.07MPa后充入氮气至压力0.1MPa， 设定温度120℃下反应2h，得到Gemini壬基酚聚氧乙烯醚4。Step 1, the synthesis of Gemini nonylphenol polyoxyethylene ether 4: the nonylphenol polyoxyethylene ether 4 is charged on the basis of 0.5mol, and 0.25mol of paraformaldehyde is added to a 500ml there-necked bottle and mixed, and vacuumed to -0.07 After MPa, nitrogen was charged to a pressure of 0.1 MPa, and the reaction was carried out at a set temperature of 120° C. for 2 h to obtain Gemini nonylphenol polyoxyethylene ether 4.
步骤2、Gemini壬基酚聚氧乙烯醚4羧酸盐的合成：将0.2mol Gemini壬基酚聚氧乙烯醚4与0.42mol马来酸酐加入到三口烧瓶中，即Gemini壬基酚聚氧乙烯醚4与马来酸酐按物质的量比为1：2.1投料，设定温度为100℃，搅拌4h。停止反应，取样用NaOH标准溶液测量酸值，计算得转化率96.03％。加入浓度为20％的氢氧化钠溶液，将产物中和至pH＝7。Step 2. Synthesis of Gemini nonylphenol polyoxyethylene ether 4 carboxylate: add 0.2mol Gemini nonylphenol polyoxyethylene ether 4 and 0.42mol maleic anhydride into the three-necked flask, namely Gemini nonylphenol polyoxyethylene The ether 4 and maleic anhydride were charged according to the material ratio of 1:2.1, the set temperature was 100°C, and the mixture was stirred for 4 hours. The reaction was stopped, the acid value was measured with NaOH standard solution by sampling, and the conversion rate was calculated to be 96.03%. The product was neutralized to pH=7 by adding 20% sodium hydroxide solution.
步骤3、Gemini壬基酚聚氧乙烯醚4磺基琥珀酸盐的合成：将上述最优工艺合成的壬基酚聚氧乙烯醚4羧酸盐按0.2mol为基准投料，加入三口烧瓶中。称取0.48mol亚硫酸氢钠，即Gemini壬基酚聚氧乙烯醚4羧酸盐与亚硫酸氢钠物质的量比为1：2.4。称取反应物总质量0.2％的硝酸钠，将催化剂硝酸钠与磺化剂亚硫酸氢钠溶于去离子水与乙醇体积比2：1的醇水溶液中，制成浓度为20％的溶液。将含有催化剂与磺化剂的溶液加入到三口烧瓶中，设定温度为100℃，回流搅拌反应8小时。反应结束后用硫代硫酸钠标准液滴定产物中剩余的亚硫酸钠，计算测定转化率为97.19％。Step 3. Synthesis of Gemini nonylphenol polyoxyethylene ether 4 sulfosuccinate: The nonylphenol polyoxyethylene ether 4 carboxylate synthesized by the above-mentioned optimal process is charged according to 0.2 mol, and added to a three-necked flask. Weigh 0.48 mol of sodium bisulfite, that is, the mass ratio of Gemini nonylphenol polyoxyethylene ether 4 carboxylate to sodium bisulfite is 1:2.4. Weigh 0.2% sodium nitrate of the total mass of the reactants, dissolve the catalyst sodium nitrate and the sulfonating agent sodium bisulfite in an alcohol aqueous solution with a volume ratio of deionized water and ethanol of 2:1 to prepare a solution with a concentration of 20%. The solution containing the catalyst and the sulfonating agent was added to a three-necked flask, the temperature was set to 100° C., and the reaction was stirred under reflux for 8 hours. After the reaction, the remaining sodium sulfite in the product was titrated with sodium thiosulfate standard titration, and the conversion rate was calculated and determined to be 97.19%.
采用上述方法制备得到的产品，在中原油田某高温高矿化度油藏进行乳化降粘(原油与注入水质量比为7:3)、油水界面张力、洗油能力检测，其中地层水样矿化度为158205mg/L，Ca
2+和Mg
2+浓度为6230mg/L，地层温度87℃，张力仪器为TX500C型转滴界面张力仪。
The products prepared by the above method were tested for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension and oil washing ability in a high-temperature and high-salinity reservoir in Zhongyuan Oilfield. The chemical degree is 158205 mg/L, the Ca 2+ and Mg 2+ concentrations are 6230 mg/L, the formation temperature is 87 °C, and the tension instrument is a TX500C transfer drop interfacial tension meter.
| 有效产品浓度，％Effective Product Concentration, % | 乳化降粘，％Emulsified viscosity reduction, % | 洗油效率，％Oil washing efficiency, % | 界面张力，mN/mInterfacial tension, mN/m | 渗透性，spermeability, s |
| 0.10.1 | 93.193.1 | 53.253.2 | 8.2×10 -3 8.2× 10-3 | 6262 |
| 0.30.3 | 94.694.6 | 59.759.7 | 6.4×10 -3 6.4× 10-3 | 4242 |
| 0.60.6 | 96.996.9 | 65.865.8 | 3.6×10 -3 3.6× 10-3 | 99 |
实施例3Example 3
一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，所述表面活性剂为Gemini异构十酚聚氧乙烯醚10磺基琥珀酸盐；A Gemini polyoxyethylene ether succinate surfactant for oil displacement, the surfactant is Gemini isomeric tenphenol polyoxyethylene ether 10 sulfosuccinate;
步骤1、Gemini异构十醇酚聚氧乙烯醚10的合成：将异构十醇酚聚氧乙烯醚10按0.5mol为基准投料，和多聚甲醛0.25mol加入到500ml三口瓶中混合，抽真空至-0.07MPa后充入氮气至压力0.1MPa，设定温度120℃下反应2h，得到Gemini异构十醇酚聚氧乙烯醚10。Step 1. Synthesis of Gemini isomerized decahydrin polyoxyethylene ether 10: The isomerized decahydrin phenol ethoxylate 10 is charged on the basis of 0.5 mol, and 0.25 mol of paraformaldehyde is added to a 500ml three-necked bottle and mixed, pumped. The vacuum was reduced to -0.07MPa and then filled with nitrogen to a pressure of 0.1MPa, and the reaction was carried out at a set temperature of 120°C for 2 hours to obtain Gemini isomerized decahydrin polyoxyethylene ether 10.
步骤2、Gemini异构十醇酚聚氧乙烯醚10羧酸盐的合成：将0.2mol Gemini异构十醇酚聚氧乙烯醚10与0.42mol马来酸酐加入到三口烧瓶中，即Gemini异构十醇酚聚氧乙烯醚10与马来酸酐按物质的量比为1：2.1投料，设定温度为100℃，搅拌4h。停止反应，取样用NaOH标准溶液 测量酸值，计算得转化率92.92％。加入浓度为20％的氢氧化钠溶液，将产物中和至pH＝7。Step 2. Synthesis of Gemini isomerized decahydrin polyoxyethylene ether 10 carboxylate: add 0.2 mol of Gemini isomerized decahydrin ethoxylate 10 and 0.42 mol of maleic anhydride into a three-necked flask, namely Gemini isomerized Decanol phenol polyoxyethylene ether 10 and maleic anhydride were charged according to the material ratio of 1:2.1, the set temperature was 100°C, and the mixture was stirred for 4 hours. The reaction was stopped, the acid value was measured with NaOH standard solution by sampling, and the conversion rate was calculated to be 92.92%. The product was neutralized to pH=7 by adding 20% sodium hydroxide solution.
步骤3、Gemini异构十醇酚聚氧乙烯醚10磺基琥珀酸盐的合成：将上述最优工艺合成的异构十醇酚聚氧乙烯醚10羧酸盐按0.2mol为基准投料，加入三口烧瓶中。称取0.48mol亚硫酸氢钠，即Gemini异构十醇酚聚氧乙烯醚10羧酸盐与亚硫酸氢钠物质的量比为1：2.4。称取反应物总质量0.2％的硝酸钠，将催化剂硝酸钠与磺化剂亚硫酸氢钠溶于去离子水与异丙醇体积比1：1的醇水溶液中，制成浓度为20％的溶液。将含有催化剂与磺化剂的溶液加入到三口烧瓶中，设定温度为100℃，回流搅拌反应8小时。反应结束后用硫代硫酸钠标准液滴定产物中剩余的亚硫酸钠，计算测定转化率为95.50％。Step 3. Synthesis of Gemini isomerized decahydrin polyoxyethylene ether 10 sulfosuccinate: the isomerized decahydrin phenol ethoxylate 10 carboxylate synthesized by the above-mentioned optimal process was fed according to 0.2 mol, and added. in a three-necked flask. Weigh 0.48mol of sodium bisulfite, that is, the mass ratio of Gemini isomerized decahydrin polyoxyethylene ether 10 carboxylate to sodium bisulfite is 1:2.4. Weigh 0.2% sodium nitrate of the total mass of the reactants, dissolve the catalyst sodium nitrate and the sulfonating agent sodium bisulfite in an alcohol aqueous solution with a volume ratio of 1:1 of deionized water and isopropanol to prepare a 20% concentration of sodium nitrate. solution. The solution containing the catalyst and the sulfonating agent was added to a three-necked flask, the temperature was set to 100° C., and the reaction was stirred under reflux for 8 hours. After the reaction, the remaining sodium sulfite in the product was titrated with sodium thiosulfate standard titration, and the conversion rate was calculated and determined to be 95.50%.
采用上述方法制备得到的产品，在胜利油田某高温高矿化度油藏进行乳化降粘(原油与注入水质量比为7:3)、油水界面张力、洗油能力检测，其中地层水样矿化度为35820mg/L，Ca
2+和Mg
2+浓度为2230mg/L，地层温度82℃，张力仪器为TX500C型转滴界面张力仪。
The products prepared by the above method were tested for emulsification and viscosity reduction (the mass ratio of crude oil and injected water was 7:3), oil-water interfacial tension, and oil washing ability in a high-temperature and high-salinity reservoir in Shengli Oilfield. The chemical degree is 35820 mg/L, the Ca 2+ and Mg 2+ concentrations are 2230 mg/L, the formation temperature is 82 °C, and the tension instrument is a TX500C transfer drop interfacial tension meter.
| 有效产品浓度，％Effective Product Concentration, % | 乳化降粘，％Emulsified viscosity reduction, % | 洗油效率，％Oil washing efficiency, % | 界面张力，mN/mInterfacial tension, mN/m | 渗透性，spermeability, s |
| 0.10.1 | 94.094.0 | 55.555.5 | 8.0×10 -3 8.0× 10-3 | 5858 |
| 0.30.3 | 95.395.3 | 61.261.2 | 6.1×10 -3 6.1× 10-3 | 3333 |
| 0.60.6 | 96.996.9 | 65.865.8 | 3.3×10 -3 3.3× 10-3 | 1010 |
对比实例5Comparative Example 5
温度对于驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的合成有重大影响，其影响主要体现在实验第一步Gemini烷基酚聚氧乙烯醚的合成上。在Gemini十五烷基酚聚氧乙烯醚9磺基琥珀酸盐实验时，进行了温度对于缩合反应产率的影响实验。Temperature has a great influence on the synthesis of Gemini polyoxyethylene ether succinate surfactant for oil displacement, and its influence is mainly reflected in the synthesis of Gemini alkylphenol polyoxyethylene ether in the first step of the experiment. In the Gemini pentadecylphenol polyoxyethylene ether 9 sulfosuccinate experiment, the effect of temperature on the yield of the condensation reaction was carried out.
Gemini十五烷基酚聚氧乙烯醚9的合成：将十五烷基酚聚氧乙烯醚9按0.2mol为基准投料，和多聚甲醛0.1mol加入到250ml三口瓶中混合，抽真空至-0.07MPa后充入氮气至压力0.1MPa，设定不同温度100℃、110℃、120℃、130℃下反应2h，得到Gemini十五烷基酚聚氧乙烯醚9。测定剩余甲醛含量，计算产率。Synthesis of Gemini pentadecylphenol polyoxyethylene ether 9: The pentadecylphenol polyoxyethylene ether 9 is charged on the basis of 0.2mol, and 0.1mol of paraformaldehyde is added to a 250ml three-necked bottle and mixed, and vacuumed to- After 0.07 MPa, nitrogen was charged to a pressure of 0.1 MPa, and the reaction was performed at different temperatures of 100 °C, 110 °C, 120 °C, and 130 °C for 2 h to obtain Gemini pentadecylphenol polyoxyethylene ether 9. The residual formaldehyde content was measured and the yield was calculated.
| 温度/℃temperature/℃ | 100100 | 110110 | 120120 | 130130 |
| 产率/％Yield/% | 95.2295.22 | 97.6097.60 | 98.7298.72 | 93.8493.84 |
由以上数据可知，在温度低于120℃时，Gemini十五烷基酚聚氧乙烯醚9的双子缩合较为容易，随温度升高产率提升，反应温度达到120℃时产率最高。超过120℃后随温度升高，产率明 显降低，显然随着温度升高出现了其他副反应，因此本例反应的最佳温度是120℃。It can be seen from the above data that the gemini condensation of Gemini pentadecylphenol polyoxyethylene ether 9 is easier when the temperature is lower than 120 °C, and the yield increases with the increase of temperature, and the yield is the highest when the reaction temperature reaches 120 °C. When the temperature exceeds 120°C, the yield decreases significantly. Obviously, other side reactions occur with the increase of temperature. Therefore, the optimum temperature for the reaction in this example is 120°C.
将上述不同温度下的产物，按实施例1步骤继续完成，合成最终产物Gemini十五烷基酚聚氧乙烯醚9磺基琥珀酸钠。将最终产品配制成有效浓度为0.3％的溶液，在胜利油田某高温高矿化度低渗油藏进行乳化降粘(原油与注入水质量比为7:3)、油水界面张力、洗油能力检测，其中地层水样矿化度为35820mg/L，Ca
2+和Mg
2+浓度为2230mg/L，地层温度90℃，张力仪器为TX500C型转滴界面张力仪。
The above-mentioned products at different temperatures are continued to be completed according to the steps of Example 1 to synthesize the final product Gemini pentadecylphenol polyoxyethylene ether 9 sodium sulfosuccinate. The final product is formulated into a solution with an effective concentration of 0.3%, and is emulsified and reduced in viscosity (the mass ratio of crude oil and injected water is 7:3), oil-water interfacial tension, and oil washing capacity in a high-temperature, high-salinity and low-permeability oil reservoir in Shengli Oilfield. In the test, the salinity of the formation water sample is 35820mg/L, the concentration of Ca 2+ and Mg 2+ is 2230mg/L, the formation temperature is 90 ℃, and the tension instrument is a TX500C transfer drop interfacial tension meter.
| 温度/℃temperature/℃ | 乳化降粘，％Emulsified viscosity reduction, % | 洗油效率，％Oil washing efficiency, % | 界面张力，mN/mInterfacial tension, mN/m | 渗透性，spermeability, s |
| 100100 | 95.495.4 | 73.273.2 | 5.1×10 -3 5.1× 10-3 | 3535 |
| 110110 | 96.196.1 | 73.973.9 | 4.8×10 -3 4.8× 10-3 | 3333 |
| 120120 | 97.397.3 | 74.874.8 | 4.3×10 -3 4.3× 10-3 | 3030 |
| 130130 | 93.993.9 | 68.668.6 | 8.9×10 -3 8.9× 10-3 | 3939 |
从对比试验可以看出，由于第一步反应转化率的影响，温度较低反应转化率不够，温度过高副产物太多最终都会影响产品的性能，因此，在第一步缩合反应的进行程度，对最终产品的性能影响至关重要应严格控制温度。It can be seen from the comparative test that due to the influence of the conversion rate of the first step reaction, the reaction conversion rate at a lower temperature is not enough, and the temperature is too high and too many by-products will eventually affect the performance of the product. Therefore, the degree of progress of the condensation reaction in the first step will be affected. , the impact on the performance of the final product is critical and the temperature should be strictly controlled.
对比实例6Comparative Example 6
采用实施例1方法制备得到的产品与十二烷基醇聚氧乙烯醚10(此处称为对比例1)，十二烷基醇聚氧乙烯醚10(30％)、十四酸甲酯(2％)、润湿剂(0.5％)复配制得驱油剂(此处称为对比例2)进行对比，在胜利油田某高温高矿化度低渗油藏进行乳化降粘(原油与驱油剂的质量比为7:3)、油水界面张力、洗油能力检测，其中地层水样矿化度为35820mg/L，Ca
2+和Mg
2+浓度为2230mg/L，地层温度90℃，张力仪器为TX500C型转滴界面张力仪，实验有效产品浓度为0.3％。
The product prepared by the method of Example 1 and lauryl alcohol polyoxyethylene ether 10 (here referred to as comparative example 1), lauryl alcohol polyoxyethylene ether 10 (30%), methyl myristate (2%) and wetting agent (0.5%) to prepare oil displacement agent (herein referred to as Comparative Example 2) for comparison, in a high temperature, high salinity and low permeability oil reservoir in Shengli Oilfield, emulsification and viscosity reduction (crude oil and The mass ratio of oil-displacing agent is 7:3), oil-water interfacial tension, and oil-washing ability detection. The salinity of the formation water sample is 35820mg/L, the concentration of Ca 2+ and Mg 2+ is 2230mg/L, and the formation temperature is 90 ℃ , the tension instrument is TX500C transfer drop interfacial tension meter, and the effective product concentration in the experiment is 0.3%.
| 实例Example | 乳化降粘，％Emulsified viscosity reduction, % | 洗油效率，％Oil washing efficiency, % | 界面张力，mN/mInterfacial tension, mN/m | 渗透性，spermeability, s |
| 实施例1Example 1 | 97.397.3 | 74.874.8 | 4.3×10 -3 4.3× 10-3 | 3030 |
| 对比例1Comparative Example 1 | 50.250.2 | 32.532.5 | 8×10 -2 8× 10-2 | ＞3min＞3min |
| 对比例2Comparative Example 2 | 95.395.3 | 68.968.9 | 1.2×10 -2 1.2× 10-2 | 21twenty one |
综上所述，本发明通过合成一系列阴-非离子表面活性剂，获得了一种全新的阴非双子表面活性剂Gemini烷基酚聚氧乙烯醚磺基琥珀酸。而且找到一条工艺路线，使其在制备时具有快速、高效、高收率、环保安全等优势，工艺的选择符合绿色化工和清洁生产的要求，不产生副 产物或废物，实现废物的“零排放”。实验表明，本发明提供的Gemini烷基酚聚氧乙烯醚磺基琥珀酸，其抗盐200000mg/L以上，抗钙镁5000mg/L以上，具有很好的推广应用前景和良好的社会经济效益。To sum up, the present invention obtains a brand-new anionic non-gemini surfactant Gemini alkylphenol polyoxyethylene ether sulfosuccinic acid by synthesizing a series of anionic-nonionic surfactants. And find a process route, so that it has the advantages of fast, high efficiency, high yield, environmental protection and safety in preparation, and the selection of process meets the requirements of green chemical industry and clean production, does not produce by-products or waste, and achieves "zero discharge of waste". ". Experiments show that the Gemini alkylphenol polyoxyethylene ether sulfosuccinic acid provided by the invention has a salt resistance of more than 200,000 mg/L, and calcium and magnesium resistance of more than 5,000 mg/L, and has a good prospect of popularization and application and good social and economic benefits.
以上所述仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above descriptions are merely examples of the present application, and are not intended to limit the present application. Various modifications and variations of this application are possible for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.
Claims (10)
- 一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，其特征在于，所述表面活性剂为Gemini烷基酚聚氧乙烯磺基琥珀酸盐，其分子通式为：A Gemini polyoxyethylene ether succinate surfactant for oil displacement, characterized in that the surfactant is Gemini alkylphenol polyoxyethylene sulfosuccinate, and its general molecular formula is:
其中M为金属离子，R为碳原子数1-20的烷基或异构烷基，n为选自3-9中的任意一个整数。wherein M is a metal ion, R is an alkyl group or an isomeric alkyl group with 1-20 carbon atoms, and n is any integer selected from 3-9. - 如权利要求1所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂，其特征在于，所述金属离子M是所述金属离子M是钠离子、钾离子和锂离子中的一种或几种。The Gemini polyoxyethylene ether succinate surfactant for oil displacement according to claim 1, wherein the metal ion M is that the metal ion M is one of sodium ion, potassium ion and lithium ion or several.
- 一种驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，将烷基酚聚氧乙烯醚和多聚甲醛混合，抽真空至-0.06Mpa～-0.08Mpa后充入氮气，加热至100℃～120℃，在压力为0.05～0.5Mpa条件下，搅拌2h；降温至70℃～100℃，加入马来酸酐，反应4～6h，用碱溶液中和至产物溶液pH＝7左右；加入含有催化剂和磺化剂的溶剂，设定转速为350r/min，在设定加热温度为70℃～100℃条件下搅拌8～10h，即得驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂。A preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement, characterized in that, the alkylphenol polyoxyethylene ether and paraformaldehyde are mixed, evacuated to -0.06Mpa～-0.08Mpa, and then charged Enter nitrogen, heat to 100℃～120℃, under the condition of pressure of 0.05～0.5Mpa, stir for 2h; cool down to 70℃～100℃, add maleic anhydride, react for 4～6h, neutralize with alkali solution to the product solution pH = about 7; add a solvent containing catalyst and sulfonating agent, set the rotation speed to 350r/min, and stir for 8 to 10 hours at a set heating temperature of 70°C to 100°C to obtain Gemini polyoxyethylene for oil displacement. Ethersuccinate surfactant.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述烷基酚聚氧乙烯醚与多聚甲醛的摩尔比为2:1。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil flooding according to claim 3, wherein the molar ratio of the alkylphenol polyoxyethylene ether to paraformaldehyde is 2:1.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，马来酸酐物质的量为烷基酚聚氧乙烯醚单体物质的量的1-1.4倍。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement as claimed in claim 3, wherein the amount of maleic anhydride substance is 1% of the amount of alkylphenol polyoxyethylene ether monomer substance -1.4 times.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述催化剂包括硝酸钠、硝酸钾和对甲苯磺酸中的一种或几种，用量为反应物总质量的0.1-0.5％。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement as claimed in claim 3, wherein the catalyst comprises one or more of sodium nitrate, potassium nitrate and p-toluenesulfonic acid , the dosage is 0.1-0.5% of the total mass of the reactants.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述磺化剂包括三氧化硫溶液、亚硫酸氢钠和亚硫酸氢钾中的一种或几种，磺化剂用量为烷基酚聚氧乙烯醚摩尔数的1.1-1.8倍。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement according to claim 3, wherein the sulfonating agent comprises sulfur trioxide solution, sodium bisulfite and potassium bisulfite One or more of the sulfonating agent dosage is 1.1-1.8 times the mole number of alkylphenol polyoxyethylene ether.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述溶剂包括碳数为1-5的醇或其与水任意比互溶的溶液。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil flooding according to claim 3, wherein the solvent comprises an alcohol with a carbon number of 1-5 or a solution that is miscible with water in any ratio .
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述碱溶液是氢氧化钠水溶液、氢氧化钾水溶液、碳酸钠水溶液和碳酸氢钾水溶液中的一种或几种。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement as claimed in claim 3, wherein the alkali solution is an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate and hydrogen carbonate One or more of potassium aqueous solutions.
- 如权利要求3所述的驱油用Gemini聚氧乙烯醚琥珀酸盐表面活性剂的制备方法，其特征在于，所述碱溶液的浓度为1％～30％。The preparation method of Gemini polyoxyethylene ether succinate surfactant for oil displacement according to claim 3, wherein the concentration of the alkaline solution is 1% to 30%.
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