CN108559471A - A kind of fluoride silicon surfactant containing three perfluoro capryls and oil-based foam oil displacement agent - Google Patents
A kind of fluoride silicon surfactant containing three perfluoro capryls and oil-based foam oil displacement agent Download PDFInfo
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- CN108559471A CN108559471A CN201810445576.7A CN201810445576A CN108559471A CN 108559471 A CN108559471 A CN 108559471A CN 201810445576 A CN201810445576 A CN 201810445576A CN 108559471 A CN108559471 A CN 108559471A
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- 239000006260 foam Substances 0.000 title claims abstract description 160
- 239000003921 oil Substances 0.000 title claims abstract description 149
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 59
- IEPMHPLKKUKRSX-UHFFFAOYSA-J silicon(4+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Si+4] IEPMHPLKKUKRSX-UHFFFAOYSA-J 0.000 title claims abstract description 57
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 56
- -1 perfluoro Chemical group 0.000 title claims abstract description 28
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 16
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005642 Oleic acid Substances 0.000 claims abstract description 16
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000002360 preparation method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 22
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 18
- 239000005052 trichlorosilane Substances 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 7
- 235000010446 mineral oil Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000005065 mining Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 22
- 238000005187 foaming Methods 0.000 abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- 239000006210 lotion Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000047 product Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 17
- 239000004088 foaming agent Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- 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
- C08G65/2639—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 elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
- C09K8/94—Foams
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
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- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Present description provides a kind of fluoride silicon surfactant containing three perfluoro capryls and oil-based foam oil displacement agents.The fluoride silicon surfactant containing three perfluoro capryls has following structure：Connect more ethyoxyls there are three perfluoro capryl and specific aggregation degree on silicon atom；It is connected with oleic acid by ester group in the other end of more ethyoxyls.It is excellent that test shows that the fluoride silicon surfactant with the structure shows in terms of foam stability energy, especially using oil as in the lotion of continuous phase.Meanwhile the surfactant also has good foam performance.Therefore, good foaming and foam stabilizing characteristic base foam flooding finish can be prepared while had using the fluoride silicon surfactant (for gas release up to 300% or more, half foam life period is more than 72h).
Description
Technical field
This specification is related to a kind of fluoride silicon surfactant containing three perfluoro capryls and oil-based foam oil displacement agent.
Background technology
Aerated fluid is applied to the history that oil field development at home and abroad has more than 40 years, and aerated fluid is in the conventional displacement of reservoir oil, tune
Drive, steam bubble drive, steam bubble handle up, cyclic steam foam flooding, the water pumping gas production of aqueous gas well, sand-flushing, drilling well, tune
It cuts open, water blockoff, acidification, all various aspects in the oil-gas field developments such as well cementing of cement and pressure break are obtained for application, and achieve affirmative
Effect.
Largely practice have shown that, foam flooding is the important means for protecting oil reservoir, preventing oil layer pollution, improving oil and gas production.
As the degree of recognition of foam technology is continuously improved in people, foam flooding means and foam flooding finish will become tertiary oil recovery
One of leading technology.
There are a large amount of hypotonic water-sensitive oil fields in the oil field in China, channel is narrow, oozes in above-mentioned oil field stratum mostly stratum
Saturating rate is extremely low, and oil reservoir is migrated difficulty in the earth formation；And it is mostly the water-sensitive formations such as montmorillonite that stratum, which is constituted, water-swellable will originally
Narrow channel block causes oil extraction operation that can not carry out.Therefore, conventional water drive or water base can not be taken for above-mentioned oil reservoir
Foam flooding.
Oil-based foam drive is the effective means to solve the above problems.Using oily (usually using diesel oil or mineral oil) as continuous phase
Foam flooding finish be referred to as oil-based foam oil displacement agent.Compared with water base foam oil displacement agent, the main spy of oil-based foam oil displacement agent
Point is energy high temperature resistance, has very strong inhibition and salt resistance, resistant to pollution ability, lubricity good, and can be effectively prevented from water drive and make
At the stratum such as montmorillonite expand passage the problem of, mitigate the damage to oil-gas Layer.
But oil phase compares that water its surface energy is extremely low, and formation of foam is difficult, and is not easy to stablize, and therefore, makes in water base oil displacement agent
The requirement to form suitable oil-based foam is not achieved in Traditional blowing agents completely.For this reason, it may be necessary to which technical staff's exploitation is directed to oil base
The suitable oil displacement agent of foam system.Currently, existing oil-based foam oil displacement agent is mainly by oil, water, foaming agent, foam stabilizer, emulsification
The compositions such as agent；System is using water as dispersed phase, and using oil as continuous media, the materials such as addition emulsifier, foaming agent, foam stabilizer are formed
Similar oils property emulsion foam system, also known as inverse emulsification foam flooding finish, grease volume ratio is at (50-80)：
The left and right (50-20).For oil-based foam oil displacement agent, gas release (foaming characteristic) and half foam life period (foam stability) are two most important
Index, technical staff exploring always scheme (the usual gas release of the gas release, half foam life period that how to improve oil displacement agent
300% or more, half-life period is likely to the application value for having certain more than 1h, it is therefore desirable to more than 10h), among these, and with foam
The raising of half-life period is problem most outstanding.For example, the formula of Tian Yunfeng et al. exploitations is：It is added 1.5% in 100ml diesel oil
AE-a and AE-b compounding foaming agent and 0.5% modified ethylene propylene ene-type polymer (PHB)；Test result is aobvious
Show, foam volume has reached 500ml (being equivalent to 500%), half-life period 353s.Heart-to-heart talk et al. exploitation formula be：In 100ml
The foam stabilizer DRI-YW-1 that 0.1% foaming agent DRI-YF-1 and 2% is added in diesel oil is the master of oil-based foam drilling fluid
Want component part；Test result shows that foam volume has reached 500ml, half-life period 630s.
Invention content
This specification is designed to provide a kind of fluoride silicon surfactant with excellent foam stability energy and oil base bubble
Foam oil displacement agent.
In order to achieve the above objectives, present description provides a kind of fluoride silicon surfactants containing three perfluoro capryls, wherein should
The structural formula of fluoride silicon surfactant is as follows：
Wherein, n 6-22.
The fluoride silicon surfactant has foam stability energy very outstanding, especially in oil-based foam system.
In above-mentioned fluoride silicon surfactant, it is preferable that n 10-18.
This specification additionally provides a kind of preparation method of the above-mentioned fluoride silicon surfactant for containing three perfluoro capryls, wherein
This approach includes the following steps：
Perfluorooctane is reacted with trichlorosilane, obtains product A；So that product A is reacted with ethylene oxide, obtains
Product B；So that product B is reacted with oleic acid, obtains the fluoride silicon surfactant.
In the above preparation method, it is preferable that perfluorooctane and the mole dosage of trichlorosilane ratio are 3：(1-1.5).
In the above preparation method, it is preferable that perfluorooctane and the mole dosage of ethylene oxide ratio are 3：(10-20).
In the above preparation method, it is preferable that perfluorooctane and the mole dosage of oleic acid ratio are 3：(1-1.2).
In the above preparation method, it is preferable that in the step of preparing product A, reaction temperature is 50-70 DEG C, when reaction
Between be 0.5-4h.
In the above preparation method, it is preferable that in the step of preparing product B, reaction temperature is 150-170 DEG C, reaction
Time is 0.5-4h.
In the above preparation method, it is preferable that in the step of making product B be reacted with oleic acid, reaction temperature 80-
120 DEG C, reaction time 0.5-4h.
In the above preparation method, it is preferable that in the step of preparing the product B, including ring-opening polymerization and take
Generation reaction, ring-opening polymerization can be acidic environment or alkaline environment.It is further preferred that the pH value of the acidic environment is
1-3.It is highly preferred that the acid used in the acidic environment is the concentrated sulfuric acid.
In the above preparation method, it is preferable that corresponding steps after reaction, terminate in the reaction of corresponding steps
Afterwards, product A and/or product B are not isolated from reaction system, continue to be fed intake into reaction system to carry out subsequent reactions.
Present description provides a kind of oil-based foam oil displacement agents, wherein includes at least one in the oil-based foam oil displacement agent
The fluoride silicon surfactant containing three perfluoro capryls of the following structural formula of kind：
Wherein, n 6-22.
The oil-based foam oil displacement agent shows very excellent half foam life period.After tested, under conventional additive amount, i.e.,
Make not using other auxiliary reagents, the half foam life period of the oil-based foam oil displacement agent has still been more than substantially 1h.
In above-mentioned oil-based foam oil displacement agent, it is preferable that n 10-18.
In above-mentioned oil-based foam oil displacement agent, it is preferable that weight of the fluoride silicon surfactant in oil-based foam oil displacement agent
Amount degree is 0.1-10%.Further preferably 1-3%.
This specification additionally provides application of the above-mentioned oil-based foam oil displacement agent in mining mineral oil；It is preferably low in exploitation
It oozes, the application in the mineral oil of water-sensitive oil field.
Description of the drawings
Fig. 1 is the infrared spectrum of three perfluoro capryl silicon-more ethyoxyl-oleates prepared by this specification experimental example 1；
Fig. 2 is the foam performance test result figure of oil-based foam oil displacement system in this specification test case 1；
Fig. 3 is the foam stability energy test result figure of oil-based foam oil displacement system in this specification test case 1；
Fig. 4 is the microscopic appearance figure of oil-based foam oil displacement system in this specification test case 1.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
This specification embodiment provides a kind of fluoride silicon surfactant containing three perfluoro capryls, the surfactant
Structural formula is as follows：
Wherein, n 6-22.
In in above structure, n represents the average value of ethoxy repeating units number, value range 6-22.Due to second
Oxygroup part is formed by epoxyethane ring-expansion polymerization, therefore its aggregate number (i.e. ethyoxyl number) has certain point
Cloth range (i.e. n values range), while according to the proportioning of reaction condition and reactant, distribution has certain variation, can be with
For integer or decimal.Specific value can be determined according to this field usual manner.
For the fluoride silicon surfactant with above structure, belong to a kind of multiple copolymer.
The fluoride silicon surfactant has special structure：Connect that there are three perfluoro capryl and specific aggregation degree on silicon atom
More ethyoxyls；It is connected with oleic acid by ester group in the other end of more ethyoxyls.Test shows that the fluorine silicon face with the structure is lived
Property agent showed in terms of foam stability energy it is excellent, especially using oil as in the lotion of continuous phase.In a specific test, by 2%
Fluoride silicon surfactant is using oil as in the lotion of continuous phase, the foam system can still keep foam volume to be more than after 72h
80%.As it can be seen that half foam life period actually can be also longer than 72h.And conventional foam stabilizer, it uses it in oil-based foam system,
The half foam life period of system often only has a few minutes, and the target from 1 hour is also poor many.As it can be seen that the fluorine that present embodiment provides
Silicon surface active agent has foam stability energy very outstanding.In addition, blistering experiment shows that (water content is the foams of 25-50%
In system), under conventional additive amount, the fluoride silicon surfactant that present embodiment provides, expansion ratio can reach 300% or more.By
This is as it can be seen that the fluoride silicon surfactant has excellent foam performance and foam stability energy, especially its excellent foam stability simultaneously
Energy.Therefore, which not only can greatly promote the half-life period of oil-based foam oil displacement agent, furthermore, it is possible to solve
Foaming agent and foam stabilizer in performance performance the problem of often mutually limiting in certainly conventional oil base foam flooding agent.Can be that oil base steeps
The developing key obstacle of foam oil displacement agent provides new solution.
Based on above-mentioned performance, fluoride silicon surfactant that present embodiment provides both can separately as Blowing agent composition with
Other agents coordinates use, and can also be used separately as foam stabilizer component and other agents coordinates；Alternatively, simultaneously as foaming
Agent component and foam stabilizer component are used with other agents coordinates；Alternatively, being used as emulsifier.
In addition, further test shows that the oil base prepared using the fluoride silicon surfactant that present embodiment provides is steeped
Foam system can obtain the foam size significantly less than conventional scheme.Microscope photo shows, the size master of foam in the system
It concentrates (overwhelming majority is in 20-30 microns) in the micron-scale.And in conventional foam system, milli subject to foam size is general
Meter level (i.e. 100 microns or more).The characteristic allow the fluoride silicon surfactant prepare oil-based foam system gap very
Small low-permeability oilfield realizes good migration, is suitable for low-permeability oilfield, this is that common foaming agent is then difficult to.
Moreover, foam size is smaller, it is less susceptible to vanish, this, which is also the fluoride silicon surfactant, has excellent foam stabilizing characteristic
One of the reason of.For example, when carrying out micro- test to foam, foam can keep former under the extruding of coverslip with the long period
Beginning foam pattern, this illustrates that the small size foam is with good stability and foamy body.This is that present embodiment provides
The another aspect advantage of fluoride silicon surfactant.Since the oil-based foam that the prior art is formed is substantially what naked eyes can be differentiated
Quasi- mm size, foamy body is not high, therefore, in micro- sem observation, due to the squeezing action of coverslip, causes foam
All rupture and can not with micro- sem observation, take pictures.In addition oil-based foam is without electric conductivity, it is difficult to electricity consumption sem observation, therefore it is rarely seen
The report of the microphoto of oil-based foam.But, this reflects in the prior art that oil-based foam intensity is low, stability is poor just
Universal present situation.
Further, in preparing oil-based foam plant process using fluoride silicon surfactant provided by the embodiment, fluorine silicon
Surfactant also presents the characteristics of it easily foams.When the foaming agent of common oil-based foam is blistered using Mechanical Method, stirring
Rotating speed need to reach 3000r/min, that is, require foaming that can must implement at high shear rates, this requirement to equipment is very
Height, most equipment cannot achieve, and the fluoride silicon surfactant generally (is preferably in 800-1500r/min as foaming component
Good foaming 1000r/min) can be realized, the requirement to shear rate is greatly reduced, and is conducive under the rough circumstances such as oil field
Implement.
Present embodiment provide fluoride silicon surfactant in, be preferably n be 10-18.The embodiment is than other
Selection has foaming characteristic more outstanding and foam stability.
Present embodiments provide for a kind of preparation method for the fluoride silicon surfactant containing three perfluoro capryls, the fluorine silicon faces
The structural formula of activating agent is：
Wherein, n 6-
22；Preparation method includes the following steps：
Perfluorooctane is reacted with trichlorosilane, obtains product A；So that product A is reacted with ethylene oxide, obtains
Product B；So that product B is reacted with oleic acid, obtains fluoride silicon surfactant.
In the preparation method that above-mentioned present embodiment provides, product A is three chlorine in trichlorosilane by perfluoro capryl
Compound after substitution；Product B is hydrogen (three perfluoro capryls to hydrogen have activation) in trichlorosilane by polyethoxy
Compound after substitution.When product B is reacted with oleic acid, the esterification of the terminal hydroxy group and oleic acid of polyethoxy can occur, from
And obtain fluoride silicon surfactant.
In the preparation method that present embodiment provides, the Conventional solvents in this field can be used.But for preferred side
Case, since main reaction raw materials perfluorooctane, trichlorosilane, ethylene oxide are all liquid, substantially can not be additional
Solvent.
In the preparation method that present embodiment provides, it can be passed through protective gas (nitrogen etc.) in reaction process, make anti-
There should be preferable yield.In addition, stirring can be usual manner, to mixing speed also without particular/special requirement.
In the preparation method that present embodiment provides, when preparing product A, raw material proportioning can be according to conventional arrangement.By
Then three substitutions are carried out to trichlorosilane, therefore, the dosage (mole) of perfluorooctane is generally three times of trichlorosilane or so.
In a preferred embodiment, perfluorooctane and the mole dosage of trichlorosilane ratio are 3：(1-1.5).The reaction condition of the step
It can also be according to conventional arrangement.In a preferred embodiment, reaction temperature can be 50-70 DEG C；Reaction time can be
0.5-4h.In most cases, this step reaction can be completed in 1-2h.In addition, the step substitution reaction is easier to carry out, without making
It also can get preferable effect with catalyst.Certainly, which is not intended to limit the use of catalyst and other auxiliary reagents.
In the preparation method that present embodiment provides, when preparing product B, it can be set according to the n values of target compound
(step reaction determines that product is a series of mixtures with different length oxyethyl chain to suitable proportioning, at this point, what n referred to
It is the average value of all molecules).In a preferred embodiment, perfluorooctane and the mole dosage of ethylene oxide ratio are 3：
(10-20).The open loop, polymerization and ethyoxyl that step reaction contains ethylene oxide are anti-to the substitution of hydrogen-based in trichlorosilane
It answers.The open loop of ethylene oxide can be acidic environment open loop or alkaline environment open loop.In a preferred embodiment, using acidity
Environment open loop.Acidic environment can select conventional inorganic acid to realize, such as the concentrated sulfuric acid.The dosage of strong acid is to reach pH value
Subject to 1-3 or so.The reaction condition of the step can be according to conventional arrangement.In a preferred embodiment, reaction temperature can be with
It is 150-170 DEG C；Reaction time can be 0.5-4h.In most cases, this step reaction can be completed in 1-2h.The reaction is simultaneously
The use of other auxiliary reagents is not limited.
In the preparation method that present embodiment provides, in the step of making product B be reacted with oleic acid, mainly make
The terminal hydroxy group of polyethoxy is esterified with oleic acid, to obtain fluoride silicon surfactant.Reaction condition and reactant dosage
It can be according to conventional arrangement.In a preferred embodiment, reaction temperature is 80-120 DEG C, reaction time 0.5-4h.
In one preferred embodiment, the mole dosage ratio of perfluorooctane and oleic acid is 3：(1-1.2).Step reaction is special without another addition
Different catalyst.Certainly, which is not intended to limit the use of catalyst and other auxiliary reagents.Terminate in the esterification of this step
Afterwards, acid or alkali neutralization is added, you can obtain fluoride silicon surfactant.Neutralization reagent can be reagent commonly used in the art.One
In preferred embodiment, to neutralize acidic environment, the basifier of selection is sodium hydroxide, potassium hydroxide.
In the preparation method that present embodiment provides, one kettle way preparation can be used, that is, terminate in the reaction of corresponding steps
Afterwards, product A and/or product B are not isolated from reaction system, continue to be fed intake into reaction system to carry out subsequent reactions.
In one preferred embodiment, this approach includes the following steps：(1) perfluorooctane is reacted into 1- with trichlorosilane at 50-70 DEG C
2h；(2) after being warming up to 150-170 DEG C after above-mentioned reaction product is acidified with strong acid, ethylene oxide the reaction was continued 1-2h is added；
(3) oleic acid is added in above-mentioned reaction product, reacts 1.5-2h；(4) it is adjusted to neutrality with sodium hydroxide.
It, generally need not be by the fluoride silicon surfactant of final step preparation in the preparation method that present embodiment provides
It isolates from reaction solution and can be used.But if it is necessary characterization is carried out, it is possible to detach in the following manner
Go out：Make fluoride silicon surfactant at salt after, n-hexane is first added by inorganic salts precipitation (add to without new precipitation generate), and
It is filtered to remove, and then vacuum distillation removes unreacted raw material and solvent at 70 DEG C, then adjusts pH value again and obtain whole production
Object.Certainly, by this kind of fluoride silicon surfactant with different n values it is completely isolated (for individual molecule) be unnecessary
And existing isolation technics it is relatively difficult to achieve.
For above-mentioned fluoride silicon surfactant, those skilled in the art can also be prepared using other suitable modes.But
It is that in comparison, the preparation method flow that this specification provides is short, it is relatively low to reaction environment requirement, and can not use
Expensive catalyst can also realize that one kettle way operates；Therefore, this method has apparent industrial advantages.
Present embodiments provide for a kind of oil-based foam oil displacement agents, wherein includes at least one in the oil-based foam oil displacement agent
The fluoride silicon surfactant containing three perfluoro capryls of the following structural formula of kind：
Wherein, n 6-22.
In the present embodiment, above-mentioned fluoride silicon surfactant is being dispersed phase oil as the emulsification foams of continuous phase using water
System has especially excellent foam stability energy.In specific test, under conventional additive amount, tried even if not using other auxiliary completely
Agent (Traditional blowing agents, foam stabilizer etc.), the foam system can still keep foam volume to be more than 80% after 72h, this is much larger than
The conventional target of 1h half-life period.
In addition, blistering experiment shows in the case where not using other auxiliary reagents completely, water content is 25-50%'s
In foam system, expansion ratio can reach 300% or more.
It can be seen that the oil-based foam oil displacement agent can have good gas release and half-life period, especially half-life period simultaneously
At least up to 72h or more.This means that can not only to solve oil-based foam oil displacement agent half-life period in this field too short for this method
Problem, but also be a kind of gas release and half-life period excellent simultaneously scheme.In the art, gas release and half-life period generally recognize
It is to be difficult to get both, for example, although two prior arts that background technology part is enumerated, the two obtain higher foaming
Amount, but half-life period is too short.In the art, also there is the scheme for attempting balance gas release and half-life period, but result is often the two
It is difficult to meet the requirements simultaneously.For example, in a United States Patent (USP), the scheme for the oil-based foam drilling fluid recorded is：In 100ml
Crude oil in be added 1% foaming agent DC-1250 and 1% foam stabilizer SV-150；Test shows that its half-life period is 4min,
But foam height is also only 180ml (gas release for being equivalent to 180%).
Existing oil-based foam oil displacement agent is often the compounding of various ingredients, and most basic is that foaming agent+foam stabilizer is (most
Emulsifier is also used in the case of number).Foaming agent mainly plays foaming effect, and foam stabilizer is mainly to delay vanishing for foam.For
Often there is repugnance in this kind of conventional oil-based foam system, individual foaming agent and foam stabilizer, this is in performance performance
The gas release and half-life period for leading to system are difficult to the main problem to get both.And the scheme that present embodiment provides, special construction
Fluoride silicon surfactant has had both two kinds of performances in same compound, to overcome above-mentioned problem.It may be fluorine silicon face
Specific structure possessed by activating agent has reconciliation effect to frothing function and foam stabilizing function.
There is the spy of good gas release and half-life period simultaneously based on the oil-based foam oil displacement agent that the above embodiment provides
Point, it is further contemplated that its unique advantage in practical applications.Due in conventional oil-based foam oil displacement agent, foaming agent and
There are larger differences in chemical constitution, functional group and polarity for foam stabilizer, and serious chromatography can occur when migrating in the earth formation
Separation, the different location being respectively in stratum so as to cause each component (or constituent content changes very greatly in each layer), is caused
Each component synergistic effect weakens, even loses, and then often results in oil-based foam agent and be unable to reach expected oil displacement efficiency.And this
The oil-based foam oil displacement agent that embodiment provides, since frothing capacity and foam stability energy are integrated in one by fluoride silicon surfactant,
What it was acted on, which plays to be acted on by stratum chromatographic isolation, is influenced, and accordingly, with respect to conventional oil base oil displacement agent, the program exists
Application has special advantage.But the oil-based foam oil displacement agent that present embodiment provides does not repel the work of fluorine silicon face
Property agent and some other conventional auxiliary reagent compounding.Under compound scheme, since fluoride silicon surfactant can still play
The effect of bubble and foam stabilizing, at least can significantly reduce influence of the chromatographic fractionation effect to oil displacement agent overall effect.
In the oil-based foam oil displacement agent that present embodiment provides, n 10-18.The embodiment has more than other selections
Gas release outstanding and half-life period.
In the oil-based foam oil displacement agent that present embodiment provides, fluoride silicon surfactant contains oil-based foam oil displacement agent
Amount can be the conventional additive amount of this field.In a preferred embodiment, fluoride silicon surfactant is in oil-based foam oil displacement agent
Weight percent content be 0.1-10%.In another embodiment, fluoride silicon surfactant is in oil-based foam oil displacement agent
Weight percent content is 1-3%.
In above-mentioned oil-based foam oil displacement agent, it is preferable that it is (low that the wax content of the oil-based foam oil displacement agent is less than 2.5%
Wax).
This specification additionally provides application of the above-mentioned oil-based foam oil displacement agent in mining mineral oil；It is preferably low in exploitation
It oozes, the application in the mineral oil of water-sensitive oil field.
Example
Following experimental example can implement the present invention for the people with general technical ability in this field or verification the verifying results provide ginseng
It examines.These examples are not limit the scope of the claims.
Experimental example 1
The trichlorosilane of 100g perfluorooctane and 11g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 50g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 25g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains packet fluorine silicon
The liquid of surfactant (three perfluoro capryl silicon-more ethyoxyl-oleates).
It after tested and calculates, more ethoxy repeating units number average value n are 16.2 in the present embodiment.
IR Characterization
Since the n values in three perfluoro capryl silicon-more ethyoxyl-oleates of preparation are a data area, molecular weight
It is not single to be analyzed as a result, extremely complex tile structure can be formed in mass spectrum, therefore, it is not suitable for Mass Spectrometric Identification；
Nuclear-magnetism also has similar problems.For this purpose, this experiment still uses the usual standard mode of this field, i.e. IR Characterization.
Before carrying out IR Characterization to three perfluoro capryl silicon of above-mentioned experimental example 1-more ethyoxyls-oleate, can by with
Under type isolates three perfluoro capryl silicon-more ethyoxyl-oleates from reaction solution：Make fluoride silicon surfactant at salt after
(sodium hydroxide is added and adjusts pH value to 7) is first added n-hexane and inorganic salts precipitation (is added to and generated without new precipitation), and mistake
It filters out, and then vacuum distillation removes unreacted raw material and solvent at 70 DEG C, then adjusts pH value again and obtain final product-
Three perfluoro capryl silicon-more ethyoxyl-oleates.Obtained infrared spectrum is shown in Fig. 1.
It is as follows to the spectrum unscrambling of infrared spectrum (Fig. 1)：
In 1170cm-1, 1260cm-1There is the asymmetric stretching vibration peak of-C-F at place, in 760cm-1, 860cm-1There is-Si-C at place
Symmetrical stretching vibration peak, thus prove that silicofluoroform has been modified to going in perfluorooctane.In 2870cm-1There are this C- for left and right
The stretching vibration of H, in 1395cm-1And 1365cm-1The bending vibration for having methyl, in 3400cm-1There are stronger-OH suctions for left and right
Peak is received, in 1700cm-1Thus the absorption peak of left and right presence-CH=O carbonyls proves that oleic acid is modified up.Therefore, above-mentioned
Infrared spectrum can prove that the product that this experimental example synthesizes is three perfluoro capryl silicon-more ethyoxyl-oleates.
Experimental example 2
The trichlorosilane of 100g perfluorooctane and 15g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 55g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 21g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains complete comprising three
The liquid of fluorine octyl silicon-more ethyoxyl-oleates.
It after tested and calculates, more ethoxy repeating units number average value n are 16.8 in the present embodiment.
Experimental example 3
The trichlorosilane of 100g perfluorooctane and 10g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 66g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 23g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains complete comprising three
The liquid of fluorine octyl silicon-more ethyoxyl-oleates.
It after tested and calculates, more ethoxy repeating units number average value n are 18.2 in the present embodiment.
Experimental example 4
The trichlorosilane of 100g perfluorooctane and 12g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 35g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 24g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains complete comprising three
The liquid of fluorine octyl silicon-more ethyoxyl-oleates.
It after tested and calculates, more ethoxy repeating units number average value n are 12.6 in the present embodiment.
Experimental example 5
The trichlorosilane of 100g perfluorooctane and 13g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 48g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 22g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains complete comprising three
The liquid of fluorine octyl silicon-more ethyoxyl-oleates.
It after tested and calculates, more ethoxy repeating units number average value n are 16.1 in the present embodiment.
Experimental example 6
The trichlorosilane of 100g perfluorooctane and 12g is placed in reactor, nitrogen protection, 60 DEG C of following stirrings are led to
The concentrated sulfuric acid (pH is made to reach 2 or so) is added in system, is warming up to 150 DEG C, is slowly added to 60g ethylene oxide, the reaction was continued by 1.5h
1.5h is cooled to 100 DEG C or so, and 22g elaidin reaction 1.5h are added, and sodium hydroxide is added and adjusts pH value to 7, obtains complete comprising three
The liquid of fluorine octyl silicon-more ethyoxyl-oleates.
It after tested and calculates, more ethoxy repeating units number average value n are 17.5 in the present embodiment.
Test case 1
Three perfluoro capryl silicon prepared by experimental example 1-more ethyoxyls-oleate prepares oil-based foam oil displacement system, specifically
For：
Fluoride silicon surfactant is added to the white oil foam system (low content of wax system) of different moisture content, carries out blistering and steady
Steep the test of performance.
Frothing capacity test is as follows：
(1) white oil is compounded with water according to different proportion, specific proportioning is：Oil/water (95/5；90/10；85/15；
80/20；75/25；70/30；65/35；60/40；55/45；50/50) solution of 10 kinds of different oil-water ratios, is obtained.
(2) the above-mentioned solution of 50mL is taken, three perfluoro capryl silicon-more second made from experimental example 1 are added in above-mentioned solution system
Oxygroup-oleate 1g.
(3) mechanical agitation realizes emulsification and foaming, stir speed (S.S.) 1000r/min, mixing time 5min simultaneously.
(4) foam system of acquisition is poured slowly into graduated cylinder, measures foam height, obtain frothing percentage result.
All of above test carries out at least parallel laboratory test three times, and test result is 3 validity test result average values.
Result is depicted as to the block diagram of water content and expansion ratio, it is specific such as Fig. 2.
From figure 2 it can be seen that when water content is more than 25%, you can reach 300% foaming of oil-based foam requirement
Multiplying power requirement.
Foam stability energy test is as follows：
The foam system that foam performance is completed to above-mentioned test carries out foam stability test, and test result is shown in Fig. 3.From Fig. 3
It can be seen that：After 72h, the foam retention of the oil based system of different moisture content still reaches 85% or more, that is, illustrates its bubble
Foam half-life period is more than 72h (requirement for being far above 1h).Its foam stability energy meets displacement of reservoir oil requirement.
Fig. 4 is the microcosmic picture (foam system that water content is 30%) when above-mentioned foam system amplifies under 100 times, can be with
Find out：
1, for the average-size of foam at 20-30 μm or so (micron order), the size is more general in the oil-based foam system
Foaming agent formed foam size it is much smaller (regular-type foam it is most subject to it is millimetre-sized i.e. be much larger than 100 microns or more), because
This compares the foam that common foaming agent is formed, and above-mentioned foam system can realize good migration in the low-permeability oilfield of gap very little,
Suitable for low-permeability oilfield, and regular-type foam system is difficult to；
2, foam can still keep original foam pattern under the extruding of coverslip, illustrate that foam has good stabilization
Property and foamy body, are conducive to the oil field displacement of reservoir oil.
Claims (10)
1. a kind of fluoride silicon surfactant containing three perfluoro capryls, which is characterized in that the structural formula of the fluoride silicon surfactant is such as
Under：
Wherein, n 6-22.
2. the fluoride silicon surfactant according to claim 1 for containing three perfluoro capryls, which is characterized in that structure above
In, n 10-18.
3. a kind of preparation method of fluoride silicon surfactant as claimed in claim 1 or 2, which is characterized in that this method include with
Lower step：
Perfluorooctane is reacted with trichlorosilane, obtains product A；
So that product A is reacted with ethylene oxide, obtains product B；
So that product B is reacted with oleic acid, obtains the fluoride silicon surfactant.
4. the preparation method of fluoride silicon surfactant according to claim 3, which is characterized in that perfluorooctane and trichlorine silicon
The mole dosage ratio of alkane is 3：(1-1.5)；
Preferably, perfluorooctane and the mole dosage of ethylene oxide ratio are 3：(10-20)；
It is further preferred that perfluorooctane and the mole dosage of oleic acid ratio are 3：(1-1.2).
5. preparation method according to claim 3, which is characterized in that in the step of preparing product A, reaction temperature is
50-70 DEG C, reaction time 0.5-4h；
Preferably, in the step of preparing product B, reaction temperature is 150-170 DEG C, reaction time 0.5-4h；
Preferably, in the step of making product B be reacted with oleic acid, reaction temperature is 80-120 DEG C, reaction time 0.5-
4h。
6. preparation method according to claim 3, which is characterized in that corresponding steps after reaction, product A and/
Or product B is not isolated from reaction system, continues to be fed intake into reaction system to carry out subsequent reactions.
7. a kind of oil-based foam oil displacement agent, which is characterized in that include at least one following structural formula in the oil-based foam oil displacement agent
The fluoride silicon surfactant containing three perfluoro capryls：
Wherein, n 6-22.
8. oil-based foam oil displacement agent according to claim 7, which is characterized in that in structure above, n 10-18.
9. oil-based foam oil displacement agent according to claim 7, which is characterized in that the fluoride silicon surfactant is steeped in oil base
The weight percent content of foam oil displacement agent is 0.1-10%；Preferably 1-3%.
10. application of the claim 7-9 any one of them oil-based foam oil displacement agents in mining mineral oil；Preferably exploiting
Application hypotonic, in the mineral oil of water-sensitive oil field.
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| CN113216917A (en) * | 2021-06-17 | 2021-08-06 | 中国石油大学(华东) | Method for controlling nitrogen channeling in oil reservoir nitrogen injection huff-puff exploitation process |
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| JPH08157819A (en) * | 1994-12-08 | 1996-06-18 | Lion Corp | Surfactant for soil improving material |
| CN102372658A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fatty alcohol-polyoxyethylene ether benzene sulfonate and preparation method thereof |
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