CN108558929A - Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds and the preparation method and application thereof - Google Patents
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds and the preparation method and application thereof Download PDFInfo
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- CN108558929A CN108558929A CN201810447996.9A CN201810447996A CN108558929A CN 108558929 A CN108558929 A CN 108558929A CN 201810447996 A CN201810447996 A CN 201810447996A CN 108558929 A CN108558929 A CN 108558929A
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- ethyoxyls
- naphthalene sulfonate
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 71
- -1 perfluoro decyl Chemical group 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003921 oil Substances 0.000 claims abstract description 68
- BPHQIXJDBIHMLT-UHFFFAOYSA-N perfluorodecane 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)C(F)(F)C(F)(F)F BPHQIXJDBIHMLT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- HUYJTJXLNBOVFO-UHFFFAOYSA-N 7-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(O)=CC=C21 HUYJTJXLNBOVFO-UHFFFAOYSA-N 0.000 claims abstract description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010792 warming Methods 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000010703 silicon Substances 0.000 claims 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 75
- 230000000087 stabilizing effect Effects 0.000 abstract description 21
- 238000007445 Chromatographic isolation Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 230000020477 pH reduction Effects 0.000 abstract description 6
- HMDPGEVMKBNYTM-UHFFFAOYSA-N FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si] 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)C(F)(F)C(F)(F)[Si] HMDPGEVMKBNYTM-UHFFFAOYSA-N 0.000 abstract description 4
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000005755 formation reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 9
- 208000002352 blister Diseases 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 0 C*(C(F)(F)F)[Si+](C)C(C)(C)* Chemical compound C*(C(F)(F)F)[Si+](C)C(C)(C)* 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- 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
- C08G65/2636—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 sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
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- Mining & Mineral Resources (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses more ethyoxyl sodium naphthalene sulfonate multi-element compounds of a kind of three perfluoro decyl silicon and the preparation method and application thereof, which by perfluoro decane, silicofluoroform, ethylene oxide and is combined to croceine acid；Preparation method includes mixing perfluoro decane with silicofluoroform, acidification, is warming up to 150~170 DEG C of addition ethylene oxide, is added after reaction to croceine acid, finally adjusts pH to 8~9.5.The multi-element compounds of the present invention are applied to carry out foam flooding in oil field.The multi-element compounds of the present invention can not only efficiently blister, and foam stabilizing effect is good, and chromatographic isolation will not occur when stratum is migrated, especially good to floorboard with high oil content (oil content 80 95%), the foam flooding effect of high wax foam system；Preparation method is simple simultaneously, and operability is strong, at low cost.
Description
Technical field
The invention belongs to foam flooding finish field, more particularly to a kind of three perfluoro decyl silicon-more ethyoxyl-sodium naphthalene sulfonates are more
First compound and the preparation method and application thereof.
Background technology
The exploitation that aerated fluid is applied to oil field at home and abroad has more than 40 years history, aerated fluid the conventional displacement of reservoir oil,
Transfer 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,
All various aspects in the oil-gas field developments such as profile control, water blockoff, acidification, well cementing of cement and pressure break are applied, and are achieved willing
Fixed 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 oil field, the big multichannel of the oil field stratum is narrow, permeability pole
Low, 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, and water-swellable will be originally narrow
Channel block causes oil extraction operation that can not carry out.Therefore, conventional water drive or water base foam can not be taken to drive the oil reservoir
Oil.
The oil-based foam displacement of reservoir oil is the effective means to solve the above problems.Using oily (usually using diesel oil or mineral oil) as continuously
The foam flooding finish of phase is referred to as oil-based foam oil displacement agent.Compared with water base foam oil displacement agent, oil-based foam oil displacement agent it is main
Feature is energy high temperature resistance, has very strong inhibition and salt resistance, resistant to pollution ability, lubricity is good, and can be effectively prevented from water drive
Caused by the stratum such as montmorillonite expansion passage the problem of, mitigate the damage to oil-gas Layer.But oil phase compares the surface of water phase
Can be extremely low, formation of foam is difficult, and is not easy to stablize, and conventional blister agent can not form oil-based foam, seriously affect oil-based foam
The development of oil displacement agent.Currently, oil-based foam oil displacement agent is mainly made of oil, water, foaming agent, foam stabilizer, emulsifier etc..System with
Water is dispersed phase, and using oil as continuous media, the materials such as addition emulsifier, foaming agent, foam stabilizer are formed by similar oils property
Emulsion foam system, also known as inverse emulsification foam flooding finish, grease volume ratio is in (50~80):(50~20) left and right.So
And with the necessary each component synergistic effect of conventional oil base foam flooding agent that emulsifier, foaming agent, foam stabilizer form, shape can be played
The purpose of oil displacement efficiency is realized at oil-based foam.Due to its in chemical constitution, functional group and polarity there are larger difference,
Serious chromatographic isolation can occur when migrating in stratum, the different location in stratum is respectively at so as to cause each component, it can not
Synergy embodies, and in turn results in oil-based foam and cannot achieve oil displacement efficiency.O ' Neil et al. have studied a kind of oil-based foam stream
Body, the oil-based foam fluid include mainly liquid control, Nephew class foaming agent, Pity vinegars, iron or lead crosslinking agent, gas etc.；Wherein liquid
It can be diesel oil, the other aliphatic hydrocarbons of kerosene person that state, which is dazzled,；Foaming agent selects fluorinated surfactant.Specific steps include：By diesel oil,
1.0%HF-2 (fiuorinated acrylic copolymer resin), 0.15%HG-2 (phosphate fat) and 0.15%HX-2 (iron adhesive) are mixed
It closes, using whisking at a high speed after device whisks 2min, gas release 47%, half-life period is more than 1h.Oil base bubble has been carried out in heart-to-heart talk et al.
The foam stabilizer DRI- of 0.1% foaming agent DRI-YF-1 and 2% is added in foam drilling fluid technical research in 100ml diesel oil
YW-1 is the chief component of oil-based foam drilling fluid, is evaluated foam volume, half-life period, rheological characteristic, as a result
Show that foam volume reaches 500ml, half-life period 630s, half-life period and foam volume reach the more excellent level in the world.But
It is that the composite request that above two oil base oil displacement agent can not meet foaming and foam stabilizing simultaneously (usually foams 300%, foam stabilizing
More than 1h).Therefore, how to reach the relative equilibrium of the two, while meeting above-mentioned requirements, have become the most important thing of research.
In addition, above-mentioned oil displacement agent is mostly mix reagent, migration in the earth formation can generate migration because of molecular results and polar difference
The difference of speed leads to chromatographic isolation phenomenon, and each component synergistic effect is caused to weaken, even lose.
In conclusion existing, there is an urgent need for one kind simply and efficiently to blister, and foam stabilizing effect is good, more particularly in the earth formation
The oil-based foam oil displacement agent that chromatographic isolation will not occur when migration, to improve hypotonic, water-sensitive oil reservoir oil recovery effect.
Invention content
Goal of the invention：The first object of the present invention be to provide it is a kind of blistering be easy, foam stability is strong, foam volume is big and
The three perfluoro decyl silicon without chromatographic isolation-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds；The second object of the present invention is to provide this
The preparation method of multi-element compounds；The third object of the present invention is to provide the application of the multi-element compounds.
Technical solution：Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=6~24.
The present invention is by using the small perfluoro decane of difference in chemical constitution, functional group and polarity, silicofluoroform, ring
The multi-element compounds of oxidative ethane and the above structure that is combined to croceine acid, enable to the compound to migrate in the earth formation
Chromatographic isolation occurs for Shi Buhui, improves oil recovery effect.Wherein, addition perfluoro decane effectively reduces the table of the multi-element compounds
Face tension realizes barbotage, and constitutes three perfluoro decyl silicon, further improves blistering of the compound when oil content is high
Effect；Addition ethylene oxide not only has the function of foam stabilizing, and has the function of helping emulsification, is improving compound foam stabilizing effect
Simultaneously further cooperateed with three perfluoro decyl silicon, efficiently solve because fluorinated volume rise, emulsifying effectiveness decline the problem of, and add
To croceine acid, emulsifiability is improved, effectively forms oil based emulsions；Silicofluoroform is added thus by perfluoro decane and ring
Oxidative ethane (ethyoxyl) is linked in a molecule compound that comes from different backgrounds and possess different abilities, and it plays perfluoro decane with high-flexibility
Steeping effect has certain facilitation.Preferably, n can be 10~18 in the multi-element compounds.
The method that the present invention prepares three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds, including walk as follows
Suddenly：Perfluoro decane is mixed with silicofluoroform, is acidified, 150~170 DEG C of addition ethylene oxide is warming up to, is added to hydroxyl after reaction
Base naphthalene sulfonic acids finally adjusts pH to 8~9.5.
Furtherly, in the preparation, the molar ratio of perfluoro decane and silicofluoroform can be 3:0.5~3.Perfluoro decane and ring
The molar ratio of oxidative ethane can be 3:5~40.Perfluoro decane with to the molar ratio of croceine acid can be 3:0.5~2.4.
Furtherly, in the preparation, the perfluoro decane with silicofluoroform of addition be react 1 under the conditions of 50~70 DEG C~
2h.Add 1~2h of reacting ethylene oxide.Addition reacts 1.5~2h to croceine acid.
Three perfluoro decyl silicon-more ethyoxyls-application of the sodium naphthalene sulfonate multi-element compounds in the displacement of reservoir oil of oil field of the present invention.
Advantageous effect：Compared with prior art, remarkable advantage of the invention is：The multi-element compounds can not only it is simple,
Efficient blistering, and foam stabilizing effect is good, and chromatographic isolation will not occur when can migrate in the earth formation, is more suitable for hypotonic, water-sensitive
Foam flooding finish in oil field, oil recovery effect is good, particularly with floorboard with high oil content (oil content 80-95%), high wax foam system
Using effect is especially prominent；Preparation method is simple simultaneously, and operability is strong, at low cost.
Description of the drawings
Fig. 1 is the infrared spectrum of multi-element compounds of the present invention；
Fig. 2 multi-element compounds using the present invention carry out the oil-based foam microscopic appearance figure when displacement of reservoir oil；
Fig. 3 is foaming effect figure of the multi-element compounds using the present invention to different moisture content miscella；
Fig. 4 is 72h foam stabilizing effect of the multi-element compounds using the present invention to different moisture content miscella.
Specific implementation mode
Technical scheme of the present invention is described in further detail below in conjunction with the accompanying drawings.
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=6~24.
The multi-element compounds prepared by the present invention carry out structural characterization, and the results are shown in Figure 1 for acquisition.In 1170cm-1, 1260cm-1There is the asymmetric stretching vibration peak of-C-F at place, in 760cm-1, 860cm-1There is the symmetrical stretching vibration of-SI-C at place
Thus peak proves that silicofluoroform has been modified to going on perfluoro decane.In 3500cm-1The stretching vibration that left and right has-OH is inhaled
Peak is received, in 1200cm-1And 1100cm-1There is the characteristic absorption peak of S=O in place.In 1600cm-1, 1500cm-1And 1450cm-1
There are 3 peaks that intensity does not wait, is the skeletal vibration absorption peak of phenyl ring, in 791cm-1, 772cm-1There is the faces C-H excurvation in place
Bent absorption of vibrations.It follows that three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds are successfully synthesized
.
Embodiment 1
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=12~18.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 9g is placed in reactor, is led to
Nitrogen protection is stirred to react 1.5h at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 40g rings
Oxidative ethane, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 14g is added, 1.5h is reacted to croceine acid；Finally, add
Enter sodium hydroxide and adjust pH value to 9, you can the multi-element compounds of the present invention are made.
When multi-element compounds prepared by the embodiment are applied to the displacement of reservoir oil, surface observation, blistering are carried out to its oil-based foam
And foam stability energy is characterized, the result of acquisition is as shown in Figures 2 to 4.As shown in Figure 2, multi-element compounds shape of the invention
At foam size much smaller far beyond the foam size that existing foaming agent is formed (present invention is substantially micron-sized bubble
Foam, and existing foam it is most subject to grade, that is, be much larger than 100 microns or more).Therefore, it is formed compared to existing foaming agent
Foam, multi-element compounds foam system of the invention can realize good migration in the low-permeability oilfield of gap very little, be suitable for
Low-permeability oilfield；And existing foaming agent is then difficult to.And the foam that the compound is formed still may be used under the extruding of coverslip
To keep original foam pattern, illustrates its with good stability and foamy body, be conducive to the oil field displacement of reservoir oil.By Fig. 3 and
For Fig. 4 it is found that the oil-based foam commonly used in the oil field displacement of reservoir oil wishes to blister multiplying power 300% or more, it is (steady that foam stabilizing half-life period is more than 1h
It steeps 50%), and the present invention can realize that can reach blistering multiplying power in water content 25% or so is more than 300%, and realize 72h
Foam stabilizing is more than 80% (i.e. the foam stabilizing time is much larger than 72h).
Embodiment 2
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=6~10.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 13g is placed in reactor,
Logical nitrogen protection, 1.5h is stirred to react at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 45g
Ethylene oxide, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 17g is added, 1.5h is reacted to croceine acid；Finally,
Sodium hydroxide is added and adjusts pH value to 8.5, you can the multi-element compounds of the present invention are made.
Embodiment 3
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=12~16.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 8g is placed in reactor, is led to
Nitrogen protection is stirred to react 1.5h at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 54g rings
Oxidative ethane, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 15g is added, 1.5h is reacted to croceine acid；Finally, add
Enter sodium hydroxide and adjust pH value to 8, you can the multi-element compounds of the present invention are made.
Embodiment 4
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=18~24.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 10g is placed in reactor,
Logical nitrogen protection, 1.5h is stirred to react at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 27g
Ethylene oxide, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 15g is added, 1.5h is reacted to croceine acid；Finally,
Sodium hydroxide is added and adjusts pH value to 9.5, you can the multi-element compounds of the present invention are made.
Embodiment 5
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=14~18.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 11g is placed in reactor,
Logical nitrogen protection, 1.5h is stirred to react at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 38g
Ethylene oxide, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 16g is added, 1.5h is reacted to croceine acid；Finally,
Sodium hydroxide is added and adjusts pH value to 8.5, you can the multi-element compounds of the present invention are made.
Embodiment 6
Three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds of the present invention, structural formula are：
Wherein, n=16~22.
Preparation method includes the following steps：First, the silicofluoroform of 100g perfluoro decanes and 10g is placed in reactor,
Logical nitrogen protection, 1.5h is stirred to react at 60 DEG C；Secondly, the concentrated sulfuric acid is added in system, is warming up to 150 DEG C, is slowly added to 50g
Ethylene oxide, the reaction was continued 1.5h；Again, 100 DEG C or so are cooled to, 16g is added, 1.5h is reacted to croceine acid；Finally,
Sodium hydroxide is added and adjusts pH value to 9, you can the multi-element compounds of the present invention are made.
Embodiment 7
Basic step is same as Example 1, the difference is that the molar ratio of perfluoro decane and silicofluoroform, specially 3:
0.25、3:0.5、3:1、3:2、1:1、3:3.5.Multi-element compounds prepared by the embodiment carry out characterization of structure and properties it is found that
Use molar ratio for 3:The multi-element compounds that 0.5~3 perfluoro decane is prepared with silicofluoroform can not only simply, efficiently rise
Bubble, and foam stabilizing effect is good, and chromatographic isolation will not occur when can migrate in the earth formation.When mole of perfluoro decane and silicofluoroform
Than being 3:When 0.25, then one side perfluoro decane price, cost increase is larger, and when molar ratio is 3:3.5 when then trifluoro silicon
Alkane can cause reaction product impurity to increase because there is autohemagglutination, and product yield reduces, and using effect declines.
Embodiment 8
Basic step is same as Example 1, the difference is that the molar ratio of perfluoro decane and ethylene oxide, specially 3:
4.5、3:5、3:10、3:20、1:10、3:40、3:45.Multi-element compounds prepared by the embodiment are carried out characterization of structure and properties can
Know, uses molar ratio for 3:The multi-element compounds that 5~40 perfluoro decane is prepared with ethylene oxide can not only be simple, efficient
Blistering, and foam stabilizing effect is good, and chromatographic isolation will not occur when can migrate in the earth formation.When rubbing for perfluoro decane and ethylene oxide
You are than being 3:When 4.5, then more ethyoxyl negligible amounts (being less than 10), cause more ethyoxyl foam stabilizing effects to decline, foam system
Stability declines, and when molar ratio is 3:When 45, then ethyoxyl quantity is more (reaching 20 or so), leads to system molecular chain length
Long, foam performance is impacted, and foamed stability is deteriorated.
Embodiment 9
Basic step is same as Example 1, the difference is that perfluoro decane and the molar ratio to croceine acid, specifically
It is 3:0.25、3:0.5、3:1、3:1.5、3:2、3:2.4、3:3.Multi-element compounds prepared by the embodiment carry out structural behaviour
Characterization is it is found that use molar ratio for 3:0.5~2.4 perfluoro decane can not only with the multi-element compounds prepared to croceine acid
Enough simple, efficient blisterings, and foam stabilizing effect is good, and chromatographic isolation will not occur when can migrate in the earth formation.Work as perfluoro decane
It is 3 with the molar ratio to croceine acid:When 0.25, then to croceine acid number deficiency, partial reaction intermediate can not be into
One step is reacted with to croceine acid, and finished product can not be made, and when molar ratio is 3:When 3, then the surface energy of reaction system is sent out
Changing, reaction carry out slowly, or even stop.
Embodiment 10
Basic step is same as Example 1, the difference is that reaction temperature when perfluoro decane is reacted with silicofluoroform,
Specially 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C.Multi-element compounds prepared by the embodiment are carried out characterization of structure and properties can
To know, the multi-element compounds that perfluoro decane is prepared with silicofluoroform under the conditions of 50~70 DEG C can not only simply, efficiently blister,
And foam stabilizing effect is good, and chromatographic isolation will not occur when can migrate in the earth formation.When perfluoro decane is reacted with silicofluoroform
When reaction temperature is less than 50 DEG C, then reaction can not carry out, and when temperature is higher than 70 DEG C, then since this reaction is exothermic reaction,
Reaction speed can be caused too fast, reaction system stability declines, and causes dangerous.
Embodiment 11
Basic step is same as Example 1, the difference is that perfluoro decane and silicofluoroform reaction time, specially
0.5h、1h、1.5h、2h、2.5h.Multi-element compounds prepared by the embodiment carry out characterization of structure and properties it is found that perfluoro decane
The multi-element compounds of 1~2h preparations are reacted with silicofluoroform simply, efficiently to blister, and foam stabilizing effect is good, can
Chromatographic isolation will not occur when migrating in the earth formation.When reaction time when perfluoro decane is reacted with silicofluoroform is less than 1h,
Then reaction cannot be carried out fully, and yield reduces, and when reacted between when being higher than 2h, then react and be basically completed, extend to be invalid
It is practical, production efficiency is reduced, is wasted time and the energy (heating).
Embodiment 12
Basic step is same as Example 1, the difference is that the reaction temperature after acidification, specially 140 DEG C, 150
℃、160℃、170℃、180℃.Multi-element compounds prepared by the embodiment are subjected to characterization of structure and properties it is found that being risen after acidification
The multi-element compounds that temperature is prepared to 150~170 DEG C can not only simply, efficiently blister, and foam stabilizing effect is good, can be on stratum
Chromatographic isolation will not occur when middle migration.When reaction temperature after acidification is less than 150 DEG C, then reacts progress slowly or even stop
Only, it is unable to get required reaction product, and when the reaction temperature after acidification is higher than 170 DEG C, then reaction speed is too fast, reaction
Heat can not be transmitted in time, and reaction controlling is difficult, even will appear danger.
Embodiment 13
Basic step is same as Example 1, the difference is that the time of reacting ethylene oxide is added, specially 0.5h,
1h、1.5h、2h、2.5h.Multi-element compounds prepared by the embodiment carry out characterization of structure and properties it is found that addition ethylene oxide is anti-
Answering multi-element compounds prepared by 1~2h can not only simply, efficiently blister, and foam stabilizing effect is good, can migrate in the earth formation
Chromatographic isolation occurs for Shi Buhui.When the time that reacting ethylene oxide is added being less than 1h, then reaction cannot be carried out fully, yield drop
It is low, and when reacted between when being higher than 2h, then react and be basically completed, extend practical to be invalid, reduce production efficiency, waste time
With the energy (heating).
Embodiment 14
Basic step is same as Example 1, the difference is that the time reacted croceine acid is added, specially
1h、1.5h、2h、2.5h.Multi-element compounds prepared by the embodiment carry out characterization of structure and properties it is found that hydroxy benzene sulfonic acid is added
Multi-element compounds prepared by 1.5~2h of reaction can not only simply, efficiently blister, and foam stabilizing effect is good, can be in the earth formation
Chromatographic isolation will not occur when migration.When the time reacted croceine acid is added less than 1.5h, then reaction cannot be abundant
Carry out, yield reduces, and when reacted between when being higher than 2h, then react and be basically completed, extend practical to be invalid, reduce production
Efficiency wastes time and the energy (heating).
By above-described embodiment it is found that the present invention three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds not
It only can simply, efficiently blister, and foam stabilizing effect is good, chromatographic isolation will not occur when can migrate in the earth formation, effect of recovering the oil
Fruit is good；Preparation method is simple simultaneously, and at low cost, operability is strong.
Claims (10)
1. a kind of three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds, it is characterised in that：The multi-element compounds
Structural formula is：
Wherein, n=6~24.
2. three perfluoro decyls silicon according to claim 1-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds, it is characterised in that：
N=10~18.
3. a kind of method preparing three perfluoro decyls silicon described in claim 1-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized by comprising following steps：Perfluoro decane is mixed with silicofluoroform, is acidified, 150~170 DEG C of addition epoxies are warming up to
Ethane is added to croceine acid after reaction, finally adjusts pH to 8~9.5.
4. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：The molar ratio of the perfluoro decane and silicofluoroform is 3:0.5~3.
5. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：The molar ratio of the perfluoro decane and ethylene oxide is 3:5~40.
6. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：The perfluoro decane is 3 with the molar ratio to croceine acid:0.5~2.4.
7. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：The perfluoro decane reacts 1~2h with silicofluoroform under the conditions of 50~70 DEG C.
8. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：1~2h of the addition reacting ethylene oxide.
9. the method according to claim 3 for preparing three perfluoro decyl silicon-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds,
It is characterized in that：Described be added reacts 1.5~2h to croceine acid.
10. three perfluoro decyls silicon described in claim 1-more ethyoxyls-sodium naphthalene sulfonate multi-element compounds are in the displacement of reservoir oil of oil field
Using.
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| CN111642515A (en) * | 2020-06-01 | 2020-09-11 | 南京师范大学 | Cyhalothrin nano slow-release pesticide preparation and preparation method thereof |
| CN112300377A (en) * | 2020-02-12 | 2021-02-02 | 中国石油天然气股份有限公司 | Alkyl-polyethoxy-sodium naphthalene sulfonate foam oil displacement agent and preparation method thereof |
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| 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300377A (en) * | 2020-02-12 | 2021-02-02 | 中国石油天然气股份有限公司 | Alkyl-polyethoxy-sodium naphthalene sulfonate foam oil displacement agent and preparation method thereof |
| CN112300377B (en) * | 2020-02-12 | 2022-06-03 | 中国石油天然气股份有限公司 | Alkyl-polyethoxy-sodium naphthalene sulfonate foam oil displacement agent and preparation method thereof |
| CN111642515A (en) * | 2020-06-01 | 2020-09-11 | 南京师范大学 | Cyhalothrin nano slow-release pesticide preparation and preparation method thereof |
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